CN113646170B - Resin sheet with support - Google Patents

Abstract

The present invention provides a resin sheet with a support for sealing an organic EL element device, which can inhibit damage to the organic EL element and deterioration of the organic EL element in a sealing process, can exhibit higher moisture barrier property, and can obtain high reliability. The resin sheet with a support is provided with 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 containing a hygroscopic filler, and at least one low-moisture-permeability layer formed of a low-moisture-permeability resin composition containing a plate-like filler, the at least one low-moisture-permeability layer being provided on the side opposite to the support with respect to the hygroscopic layer.

Description

Resin sheet with support

Technical Field

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

Background

Organic EL devices are light-emitting devices using organic substances as light-emitting materials, and are attracting attention in recent years because they can emit light with high luminance at low voltage. However, the organic EL element has very weak resistance to moisture, and has the following problems: the light-emitting material (light-emitting layer) is degraded by moisture, and the luminance is lowered, or the light is not emitted, or the interface between the electrode and the light-emitting layer is peeled off by the influence of moisture, or the metal is oxidized to have high resistance. Therefore, in order to block moisture in the element interior from the outside air, for example, the following operations are performed: the sealing layer is formed from a resin composition so as to cover the entire surface of the light-emitting layer formed on the substrate, and the organic EL element is sealed.

As a resin composition suitable for sealing applications of such an organic EL element, a resin composition containing a hygroscopic filler in the resin composition is known. For example, patent document 1 discloses a sealing resin composition containing a hygroscopic metal hydroxide, and a sealing sheet comprising a support and a resin composition layer formed from the sealing resin composition. Patent document 2 discloses a film suitable for sealing an organic EL element, which includes, as a resin composition layer, "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 moisture-absorbing filler added".

Prior art literature

Patent literature

Patent document 1: international publication No. 2017/057708

Patent document 2: international publication No. 2011/016408.

Disclosure of Invention

Problems to be solved by the invention

The resin sheets absorb moisture in the outside air by the hygroscopic layer containing the hygroscopic filler and protect the organic EL element from moisture, but the problem arises that moisture trapped by the hygroscopic filler reaches the organic EL element over time and causes deterioration, and therefore, the resin sheets cannot be said to be sufficient for sealing applications to parts of the organic EL element and the like where high moisture barrier properties (moisture resistance) are required.

The present invention has been made in view of the above-described circumstances, and an object of the present invention is to provide a resin sheet with a support having a hygroscopic layer, which is a resin sheet with a support capable of exhibiting higher moisture barrier properties.

Means for solving the problems

As a result of intensive studies to solve the above-described problems, the inventors have found that the above-described problems can be solved by providing a low moisture permeability layer on a portion side (i.e., a side opposite to the support with respect to the hygroscopic layer) where moisture entering an organic EL element or the like needs to be blocked at the time of sealing in a resin sheet constituting a support-equipped resin sheet having a hygroscopic layer, and have completed the present invention. That is, the present invention includes a scheme having the following features.

[1] A resin sheet with a support, which comprises 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

at least one low moisture permeability layer formed of the low moisture permeability resin composition,

at least one low moisture permeability layer is provided on the opposite side of the support from the moisture absorption layer,

the hygroscopic resin composition contains a hygroscopic filler,

the low moisture permeability resin composition comprises platy filler;

[2] the resin sheet with a support according to [1], wherein the content of the hygroscopic filler in the hygroscopic resin composition is 10 mass% or more and 80 mass% or less, assuming that the nonvolatile content of the hygroscopic resin composition is 100 mass%;

[3] the resin sheet with a support according to [1] or [2], wherein the content of the plate-like filler in the low moisture-permeable resin composition is 10 mass% or more and 80 mass% or less, assuming that the nonvolatile content of the low moisture-permeable resin composition is 100 mass%;

[4] the resin sheet with a support according to any one of [1] to [3], wherein the hygroscopic filler is a semi-calcined hydrotalcite;

[5] The resin sheet with a support according to any one of [1] to [4], wherein the platy filler is at least one selected from the group consisting of platy glass, uncalcined hydrotalcite, smectite (smeite) and synthetic fluorophlogopite;

[6] the resin sheet with a support according to any one of [1] to [5], wherein the average particle diameter-thickness ratio of the plate-like filler is 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-permeability layer;

[9] the resin sheet with a support according to any one of [1] to [8], wherein a ratio of a thickness of the hygroscopic layer to a thickness of the low-moisture-permeability 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 layer of the low moisture permeability layer is provided on the side opposite to the support for all the moisture absorption layers;

[11]according to [1]]～[10]The resin sheet with a support according to any one of claims, wherein the resin sheet has a water vapor permeability of 10 g/(m) ² 24 hours) or less;

[12] the resin sheet with a support according to any one of [1] to [11], wherein the hygroscopic resin composition and the low-moisture-permeability 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-permeability 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-permeability 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 support-equipped resin sheet described in any one of [1] to [16 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: the resin sheet with a support having a hygroscopic layer formed from a hygroscopic resin composition containing a hygroscopic filler can exhibit a higher moisture barrier property.

Drawings

Fig. 1 is a schematic view showing an example of a resin sheet in a resin sheet with a support according to the present invention.

Detailed Description

The resin sheet with a support of the present invention comprises a support and a resin sheet provided on the support, wherein the resin sheet has a hygroscopic layer formed from a hygroscopic resin composition and at least one layer of a low-moisture-permeability layer formed from a low-moisture-permeability resin composition, and the at least one layer of the low-moisture-permeability layer is provided on the side opposite to the support with respect to the hygroscopic layer. In a typical embodiment of the present invention, the hygroscopic resin composition contains a hygroscopic filler, and the low-moisture-permeability resin composition contains a platy filler.

< hygroscopic layer >)

The hygroscopic layer in the support-equipped resin sheet of the present invention is formed of a hygroscopic resin composition. In a typical mode of the present invention, the hygroscopic resin composition contains a hygroscopic filler.

The hygroscopic filler is not particularly limited as long as it is a filler having hygroscopicity, and examples thereof include metal oxides such as calcium oxide, magnesium oxide, calcined hydrotalcite, and layered metal hydroxides such as semi-calcined hydrotalcite. As the hygroscopic filler, calcined hydrotalcite, semi-calcined hydrotalcite, and calcium oxide are preferable, and semi-calcined hydrotalcite is particularly preferable. Although semi-calcined hydrotalcite has excellent moisture absorption performance, the problem of deterioration of the organic EL element due to trapped moisture is also remarkable, but in the present invention, the trapped moisture can be suppressed from reaching the organic EL element by the low moisture permeability layer, and therefore the moisture absorption performance of semi-calcined hydrotalcite can be fully exhibited, whereby a resin sheet with a support body that is particularly preferable from the viewpoint of moisture barrier properties can be obtained. These hygroscopic fillers may be used alone in an amount of 1 or 2 or more. The hygroscopic filler in the present invention is a filler having a saturated water absorption of 1 mass% or more, which is defined later.

The uncalcined hydrotalcite is, for example, natural hydrotalcite (Mg) ₆ Al ₂ (OH) ₁₆ CO ₃ ·4H ₂ O) is represented by a metal hydroxide having a layered crystal structure, for example, a metal hydroxide composed of a layer [ Mg ] serving as a basic skeleton _1-X Al _X (OH) ₂ ] ^X+ And an intermediate layer [ (CO) ₃ ) _X/2 ·mH ₂ O] ^X- And (5) forming. The uncalcined hydrotalcite in the present invention is a concept of hydrotalcite-like compounds including synthetic hydrotalcite and the like. Examples of the hydrotalcite-like compound include compounds represented by the following formula (I) and the following formula (II).

[M ²⁺ _1-x M ³⁺ x(OH) ₂ ] ^x+ ·[(A ^n- ) _x/n ·mH ₂ O] ^x- (I)

(wherein M ²⁺ Represents Mg ²⁺ 、Zn ²⁺ Equivalent 2 valence metal ion, M ³⁺ Represents Al ³⁺ 、Fe ³⁺ Equivalent 3 valent metal ion, A ^n- Representing CO ₃ ^2- 、Cl ^- 、NO ₃ ^- An equal n-valent anion, x is more than 0 and less than 1, m is more than or equal to 0 and less than 1, and n is a positive number. )

In the formula (I), M ²⁺ Preferably Mg ²⁺ ，M ³⁺ Preferably Al ³⁺ ，A ^n- Preferably CO ₃ ^2- 。

M ²⁺ _x Al ₂ (OH) _2x+6-nz (A ^n- ) _z ·mH ₂ O (II)

(wherein M ²⁺ Represents Mg ²⁺ 、Zn ²⁺ Equivalent 2 valent metal ion, A ^n- Representing CO ₃ ^2- 、Cl ^- 、NO ₃ ^- An equal n-valent anion, x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number.)

In the formula (II), M ²⁺ Preferably Mg ²⁺ ，A ^n- Preferably CO ₃ ^2- 。

The semi-calcined hydrotalcite is a metal hydroxide having a layered crystal structure in which the amount of interlayer water is reduced or eliminated by calcining the uncalcined hydrotalcite. The term "interlayer water" as used herein refers to "H" described in the above-mentioned composition formula of the uncalcined natural hydrotalcite and hydrotalcite-like compound ₂ O”。

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

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

The term "saturated water absorption" as used herein means: 1.5g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite was weighed by a balance, and after measuring the initial mass, the mass increase rate relative to the initial mass was obtained by the following formula (i) after standing for 200 hours in a mini environmental tester (SH-222 manufactured by ESPEC Co., ltd.) set at a temperature of 60℃and a relative humidity of 90%:

saturated water absorption (mass%) =100× (mass after moisture absorption-initial mass)/initial mass (i).

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

In addition, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the thermal weight loss ratio (thermal weight loss ratio) measured by thermogravimetric analysis. The half-calcined hydrotalcite has a thermal weight loss ratio at 280 ℃ of less than 15 mass% and a thermal weight loss ratio at 380 ℃ of 12 mass% or more. On the other hand, the thermal weight loss ratio of the uncalcined hydrotalcite at 280℃is 15 mass% or more, and the thermal weight loss ratio of the calcined hydrotalcite at 380℃is less than 12 mass%.

For thermogravimetric analysis, 5mg of hydrotalcite was weighed in an aluminum sample pan by using TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science, and the mixture was heated from 30℃to 550℃at a heating rate of 10℃per minute under an atmosphere having a nitrogen flow rate of 200 mL/min in an open state without covering. The thermal weight loss ratio can be determined by the following formula (ii):

thermal weight loss ratio (mass%) =100× (mass before heating-mass at the prescribed temperature)/mass before heating (ii).

In addition, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by peak and relative intensity ratio measured by powder X-ray diffraction. In the case of the semi-calcined hydrotalcite, a peak split into 2 peaks is shown by powder X-ray diffraction in the vicinity of 8 to 18 ° or a peak having a shoulder is shown by synthesis of two peaks, and a relative intensity ratio of a diffraction intensity of a peak or shoulder appearing on the low angle side (=low angle side diffraction intensity) to a diffraction intensity of a peak or shoulder appearing on the high angle side (=high angle side diffraction intensity) (= low angle side diffraction intensity/high angle side diffraction intensity) is 0.001 to 1,000. On the other hand, the uncalcined hydrotalcite has only one peak in the vicinity of 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side to that of the peak or shoulder appearing on the high angle side is outside the aforementioned range. The calcined hydrotalcite had no characteristic peak in the region of 8 ° to 18 °, and had a characteristic peak at 43 °. For powder X-ray diffraction measurement, a powder X-ray diffraction apparatus (Empyrean, manufactured by PANalytical Co.) was used as the counter cathode

The measurement was performed under conditions of a voltage of 45V, a current of 40mA, a sampling width of 0.0260 DEG, a scanning speed of 0.0657 DEG/S, and a diffraction angle range (2 theta) of 5.0131 DEG to 79.9711 deg. Peak search (peak search) may be carried by diffraction meansThe peak search function of the software was performed under the conditions of "minimum significance 0.50, minimum peak tip 0.01 °, maximum peak tip 1.00 °, peak base line width 2.00 °, and method of minimum value of second order differentiation".

The BET specific surface area of the hydrotalcite is preferably 1 to 250m ² Preferably 5 to 200m ² And/g. The BET specific surface area of hydrotalcite can be calculated by the BET multipoint method by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by MOUNTECH Co.).

The average particle diameter of hydrotalcite is preferably 1 to 1,000nm, more preferably 10 to 800nm. The average particle diameter of hydrotalcite is the median particle diameter of the particle size distribution when the particle size distribution is prepared by the laser diffraction scattering particle size distribution measurement (JIS Z8825) on a volume basis.

As the hydrotalcite, hydrotalcite surface-treated with a surface treatment agent can be used. As the surface treatment agent used in 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. The surface treating agent may be used in an amount of 1 or 2 or more.

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 among these, stearic acid is preferable. 1 or 2 or more of them may be used.

Examples of alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, and n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride. 1 or 2 or more of them may be used.

Examples of the silane coupling agent include epoxy silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl methyl dimethoxy silane and 11-mercaptoundecyl trimethoxy silane; amino silane coupling agents such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl dimethoxymethylsilane, N-phenyl-3-aminopropyl trimethoxysilane, N-methylaminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and N- (2-aminoethyl) -3-aminopropyl dimethoxymethylsilane; ureido silane coupling agents such as 3-ureido propyl triethoxy silane; vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styrene-based silane coupling agents such as p-styryl trimethoxysilane; acrylate silane coupling agents such as 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane; isocyanate silane coupling agents such as 3-isocyanatopropyl trimethoxysilane, sulfide silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, triazine silane, and the like. 1 or 2 or more of them may be used.

The surface treatment of hydrotalcite may be performed, for example, by: while stirring and dispersing untreated hydrotalcite at normal temperature by a mixer, a surface treating agent is added by spraying and stirring is carried out for 5 to 60 minutes. Examples of the mixer include mixers such as V-type mixers (blender), ribbon mixers (ribbon blender), double cone mixers (V-drive コ), mixers such as Henschel mixer (Henschel mixer) and concrete mixer, and mixers such as ball mills and chopper mills (cutter mill). In addition, when pulverizing hydrotalcite by a ball mill or the like, the above-mentioned higher fatty acid, alkylsilane or silane coupling agent may be added to carry out surface treatment. The amount of the surface treatment agent used varies depending on the type of hydrotalcite or the type of the surface treatment agent, and is preferably 1 to 10 parts by mass based on 100 parts by mass of hydrotalcite not subjected to surface treatment. In the present invention, the hydrotalcite subjected to the surface treatment 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 can be exerted, and the nonvolatile component of the hygroscopic resin composition is preferably 10 mass% or more and 80 mass% or less, more preferably 15 mass% or more and 78 mass% or less, still more preferably 20 mass% or more and 75 mass% or less, based on 100 mass%. When the content of the hygroscopic filler is 10 mass% or more, the hygroscopic property can be more effectively exhibited. Further, by setting the content of the hygroscopic filler to 80 mass% or less, film forming property at the time of film formation (film formation), adhesive property of the resin composition, surface smoothness and the like can be further improved.

The hygroscopic resin composition of the present invention may contain a filler other than the hygroscopic filler described above within a range that does not impair the effects of the present invention. Examples of the filler other than the hygroscopic filler include inorganic fillers such as silica, alumina, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, and silicate, and organic fillers such as rubber particles, silicone powder, nylon powder, and fluororesin powder. When the hygroscopic filler is 100% by mass, the content of the filler other than the hygroscopic filler is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and further preferably 10% by mass or less.

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

Thermosetting resin

The thermosetting resin is not particularly limited, and may be used in an amount of 1, or may be used in an amount of 2 or more, and epoxy resin is preferably used.

The epoxy resin is not limited as long as it has an average of 2 or more epoxy groups per 1 molecule. Examples of the epoxy resin include bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, aromatic glycidyl amine type epoxy resin (for example, tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl toluidine, diglycidyl aniline, and the like), alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac (phenol novolac) type epoxy resin, cresol novolac (cresol novolac) type epoxy resin, bisphenol a novolac type epoxy resin, epoxy resin having a butadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalene diol, diglycidyl etherate of phenol, and diglycidyl etherate of alcohol, and alkyl substituents, halides, and hydrides of these epoxy resins. The epoxy resin may be used in an amount of 1 or 2 or more.

The epoxy group equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and still more preferably 100 to 1,500, from the viewpoint of reactivity and the like. The "epoxy equivalent" is the gram number (g/eq) of the resin containing 1 gram equivalent of epoxy group, and can be measured according to the method defined in JIS K7236. The weight average molecular weight of the epoxy resin is preferably 5,000 or less.

Preferable examples of the epoxy resin 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.

The epoxy resin may be either liquid or solid, or may be used in combination with liquid epoxy resin and solid epoxy resin. The term "liquid" and "solid" as used herein refers to the state of an epoxy resin at ordinary temperature (25 ℃). From the viewpoints of coatability, workability, and adhesion, it is preferable that at least 10 mass% or more of the total amount of the epoxy resin used is a liquid epoxy resin. From the viewpoint of kneading property (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 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 65 mass%, based on 100 mass% of the nonvolatile component of the hygroscopic resin composition.

The content of the epoxy resin in the hygroscopic resin composition is preferably 10 to 79.9 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 65 mass%, based on 100 mass% of the nonvolatile component of the hygroscopic resin composition.

When the moisture-absorbent 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, and from the viewpoint of suppressing thermal degradation of the light-emitting element such as the organic EL element at the time of curing treatment of the hygroscopic resin composition, a substance that can cure the hygroscopic resin composition at a temperature of 140 ℃ or less (preferably 120 ℃ or less) is preferable. The curing agent may be used in an amount of 1 or 2 or more.

As the curing agent, a curing agent for epoxy resin, which is particularly preferable as a thermosetting resin, is exemplified. Examples of the curing agent include primary amine, secondary amine, tertiary amine curing agents, polyaminoamide curing agents, dicyandiamide, and organic acid dihydrazide. Among these, from the viewpoint of rapid curability, amine adduct-based compounds (manufactured by Ajicure 6-Techno Co., inc.), organic acid dihydrazide (manufactured by Ajicure VDH-J, ajicure UDH, ajicure LDH, etc. (manufactured by all of the element Fine chemical Co., ltd.), and the like are preferable.

As the curing agent in the present invention, an ionic liquid that can cure an epoxy resin at a temperature of 140 ℃ or lower (preferably 120 ℃ or lower) (i.e., a salt that can melt in a temperature range of 140 ℃ or lower (preferably 120 ℃ lower) and has a curing effect of an epoxy resin) can be particularly suitably used. The ionic liquid is preferably used in a state of being uniformly dissolved in a thermosetting resin (particularly, an epoxy resin). The ionic liquid advantageously functions to improve the moisture barrier property of the cured product of the hygroscopic resin composition.

Examples of the cations constituting the ionic liquid include ammonium cations such as imidazolium ion, piperidinium ion, pyrrolidinium ion, pyrazolium ion, guanidinium ion, and pyridinium ion; phosphonium cations such as tetraalkylphosphonium cations (e.g., tetrabutylphosphonium ions, tributylhexylphosphonium ions, etc.); sulfonium cations such as triethylsulfonium ion, and the like.

Further, examples of anions constituting the ionic liquid include: halide anions such as fluoride, chloride, bromide, iodide; alkyl sulfuric acid anions such as methanesulfonate ion; fluorochemical anions such as trifluoromethanesulfonate ion, hexafluorophosphonate ion, trifluorotris (pentafluoroethyl) phosphonate ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetate ion, tetrafluoroborate ion, and the like; phenol anions such as phenol ion (phenol ion), 2-methoxyphenol ion, and 2, 6-di-t-butylphenol ion; acidic amino acid ions such as aspartic acid ion and glutamic acid ion; neutral amino acid ions such as glycine ion, alanine ion, phenylalanine ion, etc.; n-acyl amino acid ions represented by the following general formula (1) such as N-benzoylalanine ion, N-acetylphenylalanine ion and N-acetylglycine ion; carboxylate anions such as formate ion, acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylate ion, α -lipoic acid ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion, and benzoate ion.

[ chemical formula 1]

(wherein R is a straight 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 cations are preferably ammonium cations and phosphonium cations, and more preferably imidazolium ions and phosphonium ions. The imidazolium ion is more specifically 1-ethyl-3-methylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-propyl-3-methylimidazolium ion, or the like.

The anion is preferably a phenol 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 phenol-based anion include 2, 6-di-t-butylphenol ion. Specific examples of the carboxylic acid-based anion include acetate ion, caprate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, α -lipoic acid ion, lactate ion, tartrate ion, hippurate ion, and N-methylhippurate ion, and among them, acetate ion, 2-pyrrolidone-5-carboxylate ion, formate ion, lactate ion, tartrate ion, hippurate ion, and N-methylhippurate ion are preferable, and acetate ion, N-methylhippurate 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, aspartic acid ion, glycine ion, N-acetylglycine ion, etc., and among them, N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion are preferable, and N-acetylglycine ion is particularly preferable.

As specific ionic liquids, for example, 1-butyl-3-methylimidazolium lactate, tetrabutylphosphonium-2-pyrrolidone-5-carboxylate, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium trifluoroacetate, tetrabutylphosphonium α -lipoate, tetrabutylphosphonium formate, tetrabutylphosphonium lactate, bis (tetrabutylphosphonium) tartrate, tetrabutylphosphonium maleate, tetrabutylphosphonium N-methylhippurate, benzoyl-DL-alanine tetrabutylphosphonium salt, N-acetylphenylalanine tetrabutylphosphonium salt, 2, 6-di-tert-butylphenol tetrabutylphosphonium salt, L-aspartic acid monotetrabutyl phosphonium salt, glycine tetrabutylphosphonium salt, N-acetylglycine tetrabutylphosphonium salt, 1-ethyl-3-methylimidazolium lactate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium maleate, N-methylimidazolium 1-ethyl-3-methylimidazolium tartrate, bis (1-ethyl-3-methylimidazolium) maleate, N-ethyl-3-methylimidazolium 1-methylimidazolium tartrate, particularly preferred are tetrabutylphosphonium N-acetylglycinate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium formate, 1-ethyl-3-methylimidazolium maleate, N-methyl hippuric acid 1-ethyl-3-methylimidazolium salt.

The synthesis method of the ionic liquid comprises the following steps: a precursor comprising a cationic site such as an alkylimidazolium, alkylpyridinium, alkylammonium, or alkylsulfonium ion and an anionic site containing halogen is reacted with NaBF ₄ 、NaPF ₆ 、CF ₃ SO ₃ Na、LiN(SO ₂ CF ₃ ) ₂ An anion exchange process of the waiting reaction; an acidic ester method in which an amine-based substance is reacted with an acidic ester to introduce an alkyl group and an organic acid residue becomes a counter anion; and neutralization methods in which an amine is neutralized with an organic acid to obtain a salt. In the neutralization method based on anions, cations and solvents, the anions and cations are used in equal amounts, and the solvent in the obtained reaction solution is distilled off and used as it is, or an organic solvent (methanol, toluene, ethyl acetate, acetone, etc.) may be further injected to carry out the liquidConcentrating.

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, and even more preferably 1 to 30% by mass, based on 100% by mass of the nonvolatile component of the hygroscopic resin composition. When the content is less than 0.1 mass%, sufficient curability may not be obtained, whereas when the content is more than 50 mass%, the storage stability of the hygroscopic resin composition may be impaired. When an ionic liquid is used as the curing agent for the epoxy resin, the content of the ionic liquid is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the epoxy resin (nonvolatile component), in view of the moisture barrier property of the cured product of the hygroscopic resin composition.

In the case where the moisture-absorbent resin composition contains a thermosetting resin, a curing accelerator may be contained for the purpose of adjusting the curing time or the like. Examples of the curing accelerator include an organic phosphine compound, an imidazole compound, an amine addition compound (for example, an epoxy addition compound obtained by stopping an addition reaction of a tertiary amine to an epoxy resin in the middle of the reaction), and a tertiary amine compound. Specific examples of the organic phosphine compound include TPP and TPP-K, TPP-S, TPTP-S (manufactured by North Korea chemical Co., ltd.). Specific examples of the imidazole compounds include Curezol 2MZ, 2E4MZ, C11Z, C Z-CN, C11Z-CNS, C11Z-A, 2MZOK, 2MA-OK, 2PHZ (manufactured by the four-national chemical industry Co., ltd.), and the like. Specific examples of the amine addition compound include Fujicure (manufactured by Fujicure industries, inc.). Specific examples of the tertiary amine compound include DBU-organic acid salts such as DBU (1, 8-diazabicycloo [5.4.0] undec-7-ene,1, 8-diazabicyclo [5.4.0] undec-7-ene), DBU 2-ethylhexyl acid salt and octyl acid salt, aromatic dimethylurea such as 2,4, 6-tris (dimethylaminomethyl) phenol (TAP), U-3512T (manufactured by San-Apro Co., ltd.), and aliphatic dimethylurea such as U-3503N (manufactured by San-Apro Co., ltd.). Among them, urea compounds are preferably used, and aromatic dimethylurea is particularly preferably used, from the viewpoint of moisture resistance. When the curing accelerator is used, the content of the nonvolatile component of the hygroscopic resin composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass. When the content is 0.05 mass% or more, the heat curing time tends to be shortened, and when the content is 5 mass% or less, the storage stability of the hygroscopic resin composition tends to be improved.

Thermoplastic resin or rubber-based resin

Examples of the thermoplastic resin or the rubber-based resin include polyolefin resins, polyester resins, polybutene resins, cycloolefin resins, phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyether sulfone resins, polysulfone resins, and (meth) acrylic polymers. Among these, polyolefin resins are preferable in terms of adhesion and adhesion moisture and heat resistance. The thermoplastic resin or the rubber-based resin may be used in an amount of 1 or 2 or more.

The content of the thermoplastic resin or the rubber-based resin in the hygroscopic resin composition is preferably 15 to 85% by mass, more preferably 16 to 79% by mass, and even more preferably 17 to 72% by mass, based on 100% by mass of the nonvolatile component of the hygroscopic resin composition.

Adhesion promoter

The hygroscopic resin composition of the present invention may contain a tackifier for the purpose of further improving the adhesiveness. The thickener is also called a thickener, and examples thereof include terpene resins, rosin resins, alicyclic hydrocarbon resins, aliphatic/aromatic copolymer hydrocarbon resins, aromatic hydrocarbon resins, coumarone-indene resins, and the like. The tackifier may be used in combination of 2 or more kinds. More preferable examples of the tackifier include aliphatic/aromatic copolymerized hydrocarbon resins, aromatic hydrocarbon resins, coumarone-indene resins, and the like.

The content of the tackifier in the hygroscopic resin composition of the present invention is preferably 5 to 75% by mass, more preferably 6 to 69% by mass, and even more preferably 8 to 63% by mass, based on 100% by mass of the nonvolatile component of the hygroscopic resin composition.

Examples of commercially available tackifiers include: ARKON P-90, ARKON P100, ARKON P115, ARKON P125, PINECRYSTAL ME-G, PINECRYSTAL ME-H, PINECRYSTAL ME-G, JXTG energy company T-REZ RB093, T-REZ RC115, neopolyer L90, neopolyer 120, neopolyer 140, T-REZ HA-105, petcoal 120, petrock 90HS, petrotack 100V, NOVARES C9, NOVARES L, nitto RESIN L-5, NITTO RESIN V-120S, NITTO RESIN G-90, etc. from the Kingchu chemical industries, inc.

Diluent agent

The hygroscopic resin composition of 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 at a temperature of 25℃is preferably 0.1 to 5000 mPas, more preferably 0.1 to 2500 mPas, still more preferably 0.1 to 1000 mPas.

As the diluent, a reactive diluent (reactive diluent) is preferable. As the reactive diluent, a compound having 1 ethylenically unsaturated group in 1 molecule (hereinafter, sometimes simply referred to as "monofunctional ethylenically unsaturated compound") is preferable. As the ethylenically unsaturated group, (meth) acryl is preferable, and in particular, for the reactive diluent, (meth) acrylate having 1 (meth) acryl in 1 molecule (hereinafter, sometimes simply referred to as "monofunctional (meth) acrylate") is more preferable.

Regarding the monofunctional (meth) acrylate used as the diluent, examples thereof include "ODA-N" (octyl/decyl acrylate, i.e., a monofunctional acrylate having a long chain alkyl group), made by DAICEL-ALLNEX corporation, "EBECRYL 110", "EBECRYL 1114" (ethoxylated phenyl acrylate), made by Kyowa chemical corporation, "Light Ester E" (ethyl methacrylate), "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), and "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" (benzylphenoxyethyl methacrylate), "Light Ester IB-X" (isobornyl methacrylate), "Light Ester HO-250" (2-hydroxyethyl methacrylate), "Light Ester HOA" (2-hydroxyethyl acrylate), "Light Ester G" (glycidyl methacrylate), "Light Acrylate IAA" (isoamyl acrylate), that is, monofunctional Acrylate having branched alkyl group), "ight Acrylate S-A" (stearyl Acrylate), "ight Acrylate EC-A" (ethoxy-diethylene glycol Acrylate), "ight Acrylate EHDG-AT" (2-ethylhexyl-diethylene glycol Acrylate), "ight Acrylate DPM-A" (methoxy dipropylene glycol Acrylate), "ight Acrylate IB-XA" (isobornyl methacrylate, that is, monofunctional methacrylate having alicyclic group), "ight Acrylate PO-A" (phenoxyethyl Acrylate, that is, monofunctional Acrylate having aromatic ring), "ight Acrylate P2H-A" (phenoxydiethylene glycol Acrylate), ight Acrylate P2H-A "ight Acrylate P-200A" (phenoxy-polyethylene glycol Acrylate), "ight Acrylate POB-A" (M-phenoxybenzyl Acrylate), "ight Acrylate TFH-A" (tetrahydrofurfuryl Acrylate), "ight Ester HOP-A (N)" (2-hydroxypropyl Acrylate), "HOA-MS (N)" (2-acryloyloxyethyl succinate), "Epoxyester M-600A" (2-hydroxy-3-phenoxypropyl Acrylate), "IDAA" (isodecyl Acrylate), "Viscoat #155" (cyclohexyl Acrylate), "Viscoat #160" (benzyl Acrylate), and "Viscoat #160" manufactured by Osakse:Sup>A organic chemical industry Co., td.), "Viscoat #150" (tetrahydrofurfuryl acrylate), "Viscoat #190" (ethylcarbitol acrylate), "OXE-10" (3-ethyl-3-oxetanylmethyl acrylate) that is an acrylate having an oxetane ring, "MEDOL-10" (2-methyl-2-ethyl-1, 3-dioxolan-4-yl acrylate that is an acrylate having a dioxolane), "Aronix M-101A" (phenol EO modified acrylate) manufactured by Toshida Synthesis company, "NK Ester A-LEN-10" (ethoxylated o-phenylphenol acrylate), "NK Ester-4E" (ethoxylated ethylhexyl polyethylene glycol methacrylate), hitachi to "FA-511AS" (dicyclopentanyl acrylate), "FA-512AS" (dicyclopentanyl acrylate) that is a dicyclopentanyloxy ethyl acrylate), "FA-513AS" (dicyclopentanyl acrylate), arkeSR "4-8-2, 3-35 (3-35) that is a catalyst" CD-3, 3-35 ", 3-35 (methyl methacrylate) that is a catalyst" 3, 3-35 "tri-35" (methyl methacrylate) that is a catalyst "3, 3-35" (tri-ethoxymethyl acrylate) that is a catalyst "3-35" (3, 3-ethoxymethyl methacrylate) that is a catalyst "3-35" (ethoxymethyl methacrylate) of new chemical industry company "VEEM" (2-ethyleneoxyethoxy) ethyl methacrylate) and the like. By "octyl/decyl acrylate" is meant a mixture of octyl acrylate and decyl acrylate.

As the monofunctional (meth) acrylate used as the diluent, a monofunctional methacrylate having an alicyclic structure is particularly preferable. The alicyclic structure is synonymous with the foregoing. Examples of the commercially available monofunctional (meth) acrylate having an alicyclic structure include: "Light Ester IB-X" (isobornyl methacrylate) manufactured by Kagaku corporation having a camphan ring (borne ring) structure, "Light Acrylate IB-XA" (isobornyl methacrylate), "Light Ester CH" (cyclohexyl methacrylate) manufactured by Kagaku corporation having a cyclohexyl structure, "Viscoat#155" (cyclohexyl acrylate) manufactured by Osaka organic chemical industry company, "SR217NS" (4-t-butylcyclohexanol acrylate), "SR420NS" (3, 5-trimethylcyclohexanol acrylate), "CD421" (3, 5-trimethylcyclohexanol acrylate), "CD535" (dicyclopentadiene methacrylate), "FA-511" (AS "(dicyclopentenyl acrylate)," FA-512 "(AS" (dicyclopentenyl acrylate), "dicyclopentenyloxyethyl acrylate)," FA-AS "(dicyclopentyl acrylate)," CD 217NS "(acrylonitrile) manufactured by Arkema corporation), and" ethyl acrylate "2- (vinyl ethyl acrylate)," 2- (vinyl ethyl acrylate) manufactured by Hitachi chemical industry company.

When the diluent is used, the content of the nonvolatile component of the hygroscopic resin composition is preferably 2 mass% or more, more preferably 5 mass% or more, still more preferably 10 mass% or more, preferably 60 mass% or less, more preferably 55 mass% or less, still more preferably 50 mass% or less, based on 100 mass%.

Silane coupling agent

Examples of the silane coupling agent include: epoxy silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl (dimethoxy) methylsilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane; mercapto silane coupling agents such as 3-mercaptopropyl trimethoxy silane, 3-mercaptopropyl triethoxy silane, 3-mercaptopropyl methyl dimethoxy silane and 11-mercaptoundecyl trimethoxy silane; amino silane coupling agents such as 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl dimethoxymethylsilane, N-phenyl-3-aminopropyl trimethoxysilane, N-methylaminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane and N- (2-aminoethyl) -3-aminopropyl dimethoxymethylsilane; ureido silane coupling agents such as 3-ureido propyl triethoxy silane; vinyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane; styrene-based silane coupling agents such as p-styryl trimethoxysilane; acrylate silane coupling agents such as 3-acryloxypropyl trimethoxysilane and 3-methacryloxypropyl trimethoxysilane; isocyanate silane coupling agents such as 3-isocyanatopropyl trimethoxysilane; sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide; phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, triazine silane, and the like. Among these, an acrylate-based silane coupling agent is preferable. The silane coupling agent may be used in an amount of 1 or 2 or more.

As the commercially available silane coupling agent, for example, "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", "KBM-5803" manufactured by Xinyue chemical Co., ltd.

When the silane coupling agent is used, the content of the nonvolatile component of the hygroscopic resin composition is preferably 0.10 to 5.00 mass%, more preferably 0.25 to 3.00 mass%, and even more preferably 0.30 to 2.00 mass% based on 100 mass%.

Other ingredients

The hygroscopic resin composition of the present invention may contain other components than the above components within a range that does not impair the effects thereof. Examples thereof include thickeners such as Orben and Benton; silicone-based, fluorine-based, polymer-based defoamers or leveling agents; adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; etc.

The hygroscopic layer in the support-equipped resin sheet of the present invention may have a multilayer structure formed of a plurality of hygroscopic layers having different compositions (for example, different types of hygroscopic fillers, different contents of hygroscopic fillers, etc.).

< Low moisture permeability layer >)

The low moisture permeability layer in the support-equipped resin sheet of the present invention is formed of a low moisture permeability resin composition. In a typical embodiment of the present invention, the low moisture permeability resin composition contains a platy filler.

The plate-like filler is not particularly limited as long as it is plate-like and can exert the effect of the present invention, and the plate-like filler in the present invention does not include hygroscopic filler. That is, the platy filler in the present invention is a platy filler having a saturated water absorption of less than 1 mass%. Examples of the plate-like filler include plate-like glass (e.g., a glass, C glass, and E glass), uncalcined hydrotalcite, and layered silicate minerals. Examples of the layered silicate mineral include: kaolinite, halloysite (halloysite), talc, smectite, mica, and the like. Among the mica, synthetic fluorophlogopite is preferred from the viewpoint of making transparency excellent. The plate-shaped filler is preferably plate-shaped glass, uncalcined hydrotalcite, smectite, or synthetic fluorophlogopite because it has a high particle diameter-to-thickness ratio (aspect ratio), exhibits low moisture permeability, and is excellent in transparency. These plate-like fillers may be used alone in an amount of 1 or in an amount of 2 or more.

The content of the plate-like filler in the low moisture-permeable resin composition is not particularly limited as long as the effect of the present invention can be exerted, and the nonvolatile content of the low moisture-permeable resin composition is preferably 10 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, based on 100 mass%. By setting the content of the plate-like filler to 10 mass% or more, the effect of low moisture permeability can be more effectively exhibited. Further, by setting the content of the plate-like filler to 80 mass% or less, film forming property at the time of film formation, adhesion property of the resin composition, surface smoothness and the like can be further improved.

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

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

The average thickness of the plate-like filler can be measured by the following method. The thicknesses of 100 particles were measured using a Scanning Electron Microscope (SEM), and the average value was calculated from these measured values. In this case, each particle can be observed and measured by a scanning electron microscope, a filler (particle group) is filled in a resin, the resin is molded, and the molded product is broken, and the broken surface can be observed and measured. In any measurement method, the sample stage of the scanning electron microscope is adjusted by the sample stage micro-motion 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 diameter of the plate-like filler is preferably 0.05 μm or more, more preferably 0.1 μm or more, and still more preferably 2 μm or more. From the viewpoint of transparency, it is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less.

The average particle size of the platy filler can be determined using a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by: the particle size distribution of the filler was prepared based on volume by using a laser diffraction type particle size distribution measuring apparatus, and the median particle size was used as the average particle size. For the measurement sample, a product obtained by dispersing the filler in water by ultrasonic waves can be preferably used. As the laser diffraction scattering particle size distribution measuring apparatus, LA-500 manufactured by horiba, inc. can be used.

The low moisture permeability resin composition in the present invention may contain fillers other than the above-mentioned platy fillers within a range that does not impair the effects of the present invention. When the plate-like filler is set to 100 mass%, the content of the filler other than the plate-like filler is preferably 50 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, and further preferably 10 mass% or less.

The resin constituting the low moisture permeability resin composition in the present invention is not particularly limited as long as the effect of the present invention can be exerted, and examples thereof include thermosetting resins, thermoplastic resins, rubber-based resins, and the like. The thermosetting resin, thermoplastic resin, and rubber-based resin are the same as those described for the hygroscopic layer. The low moisture permeability resin composition of the present invention may contain the components described above with respect to the moisture absorption layer.

The low moisture-permeable layer in the support-equipped resin sheet of the present invention may have a multilayer structure formed of a plurality of layers of different compositions (for example, different types of plate-like fillers, different amounts of plate-like fillers, different average particle diameter/thickness ratios of plate-like fillers, etc.).

< resin sheet >)

The resin sheet of the support-equipped resin sheet of the present invention has at least one hygroscopic layer and at least one low-moisture-permeability layer as described above. The resin sheet has at least one low moisture permeability layer on the side opposite to the support with respect to the moisture absorption layer. It is presumed that by providing the resin sheet with such a structure, the movement of moisture trapped in the hygroscopic layer can be blocked by the low-moisture-permeability layer, and as a result, the resin sheet with the support that can exhibit higher moisture barrier properties can be obtained.

The thickness of the resin sheet is not particularly limited as long as the effects of the present invention can be exerted, and is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 80 μm or less. When the thickness of the resin sheet is 5 μm or more, film forming property of the film, adhesion property of the resin composition, and the like can be further improved. In addition, when the thickness is 100 μm or less, the contact area between the side surface of the resin sheet and the outside air is also reduced, and the invasion of moisture can be more effectively suppressed.

The thickness of the hygroscopic layer is not particularly limited as long as the effect of the present invention can be exerted, and is preferably 2.5 μm or more and 95 μm or less, more preferably 5 μm or more and 50 μm or less. The thickness of the low moisture permeability layer is not particularly limited as long as the effect of the present invention can be exerted, and is preferably 0.25 μm or more and 50 μm or less, more preferably 2.5 μm or more and 50 μm or less.

In the resin sheet, the thickness of the hygroscopic layer is preferably equal to or greater than the thickness of the low moisture permeability layer, and for example, the ratio of the thickness of the hygroscopic layer to the thickness of the low moisture permeability layer is preferably 1.0 to 20, more preferably 1.5 to 15. By setting the ratio to 1.0 or more (that is, by making the hygroscopic layer thicker than the low-moisture-permeability layer), the hygroscopic property can be more effectively exhibited, and by setting the ratio to 20 or less, the low-moisture-permeability property by the low-moisture-permeability layer can be more effectively exhibited.

The water vapor permeability of the resin sheet in the support-equipped resin sheet of the present invention is preferably 10 g/(m) ² 24 hours) or less. The water vapor permeability is more preferably 5 g/(m) ² 24 hours) or less. The water vapor permeability of the resin sheet was obtained by an infrared sensor method according to JIS K7129B at a temperature of 40℃under an atmosphere having a relative humidity of 90%. As a water vapor permeability measuring device using an infrared sensor method according to JIS K7129B, there can be mentioned film health And a water vapor permeability measuring device (PERMATRAN-W3/34) manufactured by MOCON, inc.

The resin sheet of the support-equipped resin sheet of the present invention has at least one hygroscopic layer and at least one low moisture permeability layer. At least one low moisture permeability layer is disposed on the opposite side of the hygroscopic layer from the support. From the viewpoint of exhibiting higher moisture barrier properties, it is preferable that at least one layer of low moisture permeability is provided on the side opposite to the support for all the moisture absorption layers. The resin sheet of the present invention may have one or more layers (for example, any resin composition layer) at any position other than the hygroscopic layer and the low-moisture-permeability layer within a range where the effects of the present invention can be exerted. In addition, the resin sheet with a support of the present invention may have a cover film on a surface of the resin sheet opposite to the support side. The layer structure in the support-equipped resin sheet of the present invention may be, for example, the following:

(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 permeability layer + cover film

(4) Support, hygroscopic layer, low moisture permeability layer, hygroscopic layer, cover film

The coating film is peeled off and applied to sealing parts and the like in sealing parts and the like where high moisture barrier properties are required, such as organic EL elements. In the above-described layer structure (4), the moisture trapped in the hygroscopic layer on the side of the support can be restrained from moving to the portion where moisture barrier property is required by using the low-moisture-permeability layer, but the moisture trapped in the hygroscopic layer on the side of the cover film is not restrained but can move, so that it is preferable to form a layer structure in which at least one low-moisture-permeability layer is provided on the side opposite to the support for all the hygroscopic layers as in the layer structures (1) to (3).

< resin sheet with support >)

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

Examples of the support include a plastic film such as polyolefin such as Polyethylene and Polypropylene (PP), polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), cyclic Olefin Polymer (COP), and polyvinyl chloride. The plastic film may be used in an amount of 1 kind or 2 or more kinds. The support is preferably a PET film, PEN film or COP film, more preferably a PET film.

In order to improve the moisture resistance (moisture resistance) of the resin sheet, a plastic film having a barrier layer may be used as a support. The barrier layer may or may not be in contact with the hygroscopic layer of the resin sheet (i.e., for example, the barrier layer may be formed on the surface of the support opposite to the surface of the support in contact with the hygroscopic layer of the resin sheet). Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, metal foils such as stainless steel foil and aluminum foil. The barrier layer may be a multilayer structure of 2 or more layers. Examples of the plastic film having the barrier layer include films of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin polymer, and the like. The plastic film may have a multilayer structure of 2 or more layers. The plastic film having the barrier layer may be commercially available. Examples of the commercial products of the polyethylene terephthalate film with aluminum foil include "Al with PET (1N 30)" manufactured by eastern ocean aluminum vending company, and "Al 3025 with PET" manufactured by fofield metals company.

For example, when the resin sheet with a support of the present invention is used for a display, a polarizing plate or the like can be used as the support. 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 product obtained by bonding a plastic film having a barrier layer to a polarizing plate with an adhesive such as an optical adhesive sheet (OCA) may be used as the support. In this case, the resin sheet with the support has a structure in which the plastic film having the barrier layer is in contact with the resin sheet.

The support may be subjected to a mold release treatment, a matting treatment, a corona treatment, or the like based on 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. The lower limit of the thickness of the support is preferably 10 μm, more preferably 20 μm, and the upper limit is preferably 200 μm, more preferably 125 μm, from the viewpoint of handleability and the like. The preferred ranges of the thickness of the support (i.e., the combination of the preferred upper and lower limits) are (i) 10 to 200 μm, (ii) 20 to 200 μm, (iii) 10 to 125 μm, and (iv) 20 to 125 μm.

The resin sheet with a support of the present invention may have a cover film on the side of the resin sheet opposite to the support side. As such a cover film, a film similar to a plastic film of a support can be given. 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 still more preferably a PET film. The cover film may be subjected to a mold release treatment, a matting treatment, a corona treatment, or the like based on 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 multilayer structure of 2 or more layers. The thickness of the cover film is not particularly limited. 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 from the viewpoints of handleability, drying of the resin sheet, and the like. The preferable ranges of the thickness of the cover film (i.e., combinations of preferable upper and lower limits) are (i) 10 to 200 μm, (ii) 20 to 200 μm, (iii) 10 to 125 μm, and (iv) 20 to 125 μm.

< electronic device >)

An electronic device in which an electronic component is sealed with the support-equipped resin sheet of the present invention can be manufactured, for example, by laminating the support-equipped resin sheet of the present invention on an electronic component on a substrate.

Examples

The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples, and it is needless to say that the present invention can be implemented by appropriately applying modifications within a range suitable for the gist described above and below, and all of them are included in the technical scope of the present invention. Unless otherwise specified, "%" in the amounts described below means "% by mass".

< manufacturing example 1 >

Varnishes of the compounding ratios shown in the following table 1 were prepared according to the following procedures. A mixture was obtained by dispersing maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Mitsubishi Co., ltd.), polybutene (HV-1900, manufactured by Mitsubishi Co., ltd.) and semi-calcined hydrotalcite (hygroscopic filler; DHT-4C, manufactured by Co., ltd.) in a saturated hydrocarbon resin (tackifier; ARKON P125) containing cyclohexane ring in SWASOL so that the solid content became 60%. The resultant mixture was blended with a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP 341 (manufactured by the company PMC, star light), SWASOL solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by the company Kayaku Akzo) and toluene, and the resultant mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of a hygroscopic resin composition.

< manufacturing example 2 >

Varnishes of the compounding ratios shown in the following table 1 were prepared according to the following procedures. A mixture was obtained by dispersing maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Mitsubishi Co., ltd.), polybutene (HV-1900, manufactured by Mitsubishi Co., ltd.) and synthetic fluorophlogopite (platy filler; PDM-5B, manufactured by TOPY Industrial Co., ltd.) in a product obtained by dissolving a saturated hydrocarbon resin (tackifier; ARKON P125) containing cyclohexane ring in SWASOL so that the solid content became 60%. The resultant mixture was blended with a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP 341 (manufactured by the company PMC, star light), SWASOL solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by the company Kayaku Akzo) and toluene, and the resultant mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of a low-moisture-permeability resin composition.

< manufacturing example 3 >

Varnishes of the compounding ratios shown in the following table 1 were prepared according to the following procedures. A mixture was obtained by dispersing maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Star PMC Co., ltd.), polybutene (HV-1900, manufactured by Star PMC Co., ltd.) and plate-like glass filler (FTD 010-F01, manufactured by Nitro Japan Co., ltd.) in a product obtained by dissolving a saturated hydrocarbon resin (tackifier; ARKON P125) containing a cyclohexane ring in SWASOL so that the solid content became 60%. The resultant mixture was blended with a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP 341 (manufactured by the company PMC, star light), SWASOL solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by the company Kayaku Akzo) and toluene, and the resultant mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of a low-moisture-permeability resin composition.

< manufacturing example 4 >

Varnishes of the compounding ratios shown in the following table 1 were prepared according to the following procedures. A mixture was obtained by dispersing maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Star PMC Co., ltd.), polybutene (HV-1900, manufactured by Star PMC Co., ltd.) and smectite (platy filler; sumecton SAN, manufactured by Kunimine Co., ltd.) in a product obtained by dissolving a saturated hydrocarbon resin (tackifier; ARKON P125) containing cyclohexane rings in SWASOL so that the solid content became 60%. The resultant mixture was blended with a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP 341 (manufactured by the company PMC, star light), SWASOL solution, solid content 20%), an anionic polymerization type curing agent (TAP, manufactured by the company Kayaku Akzo) and toluene, and the resultant mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of a low-moisture-permeability resin composition.

< manufacturing example 5 >

Varnishes of the compounding ratios shown in the following table 1 were prepared according to the following procedures. A saturated hydrocarbon resin (thickener; ARKON P125) containing a cyclohexane ring was dissolved in SWASOL to obtain a product having a solid content of 60%, and then a maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Star PMC), polybutene (HV-1900, manufactured by Star PMC), a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP 341 (manufactured by Star PMC)), a SWASOL solution, a solid content of 20%, an anionic polymerization curing agent (TAP, manufactured by Kayaku Akzo) and toluene were mixed and the obtained mixture was uniformly dispersed by a high-speed rotary mixer to obtain a varnish of a resin composition.

TABLE 1

Example 1 >

The varnish obtained in production example 1 was uniformly applied to the release treated surface of a PET film "SP3000" (PET: 35 μm: trade name manufactured by Toyo Cloth Co., ltd.) treated with a silicone-based release agent by a die coater, and heated at 130℃for 60 minutes, thereby providing a hygroscopic layer having a thickness of 25 μm;

the varnish obtained in production example 2 was uniformly applied to a release treated surface of a PET film "SP4020" (PET: 50 μm: trade name of Toyo Cloth Co., ltd.) treated with a silicone-based release agent by a die coater, and heated at 130℃for 60 minutes, thereby providing a low moisture permeability layer having a thickness of 15 μm;

the hygroscopic layer was laminated with a low moisture permeability layer using a batch vacuum laminator (manufactured by Nichigo-Morton company, V-160) to obtain a resin sheet with a support. The lamination conditions were: after a pressure reduction time of 30 seconds at 80℃a pressure of 0.3MPa was applied 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. Mu.m.

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-permeability layer was 25 μm.

Example 4 >

In example 1, a resin sheet with a support was obtained in the same manner except that the varnish obtained in production example 3 was used instead of the varnish obtained in production example 2 to obtain a low moisture permeability layer.

Example 5 >

In example 1, a resin sheet with a support was obtained in the same manner except that the varnish obtained in production example 4 was used instead of the varnish obtained in production example 2 to obtain a low moisture permeability layer.

Comparative example 1 >

The varnish obtained in production example 1 was uniformly applied to the release treated surface of a PET film "SP3000" (PET: 35 μm: trade name manufactured by Toyo Cloth Co.) treated with a silicone-based release agent by a die coater, and heated at 130℃for 60 minutes, whereby a resin sheet with a support having only a hygroscopic layer with a thickness of 25 μm was obtained.

Comparative example 2 >

The varnish obtained in production example 2 was uniformly applied to the release treated surface of a PET film "SP4020" (PET: 50 μm: trade name of Toyo Cloth Co.) treated with a silicone-based release agent by a die coater, and heated at 130℃for 60 minutes, whereby a resin sheet with a support having only a low moisture permeability layer having a thickness of 25 μm was obtained.

Comparative example 3 >

In example 1, a resin sheet with a support was obtained in the same manner except that the varnish obtained in production example 5 was used instead of the varnish obtained in production example 2 to obtain a low moisture permeability layer.

Device reliability test (light emitting area reduction rate) >

The sealability (barrier property) of the resin sheet against moisture penetrating from the frame was evaluated using the organic EL element. Specifically, first, the light-emitting area was set to 4mm ² An organic EL element (thickness of organic film: 110nm, thickness of Al cathode: 100 nm) is formed on a glass substrate (manufactured by GEOMATEC Co.) with Indium Tin Oxide (ITO);

next, the PET film on the hygroscopic layer side of the resin sheets with support (length: 25mm, width: 15 mm) produced in examples and comparative examples was peeled off, and an aluminum foil/PET composite film "AL 1N30 with PET" (aluminum foil: 30 μm, PET:25 μm; trade name manufactured by Toyo-Albah Co., ltd.) as a support was laminated on the hygroscopic layer using a batch vacuum laminator (manufactured by Nichigo-Morton Co., ltd., V-160), to obtain another resin sheet with support. The lamination conditions were: after a pressure reduction time of 30 seconds at 80℃a pressure of 0.3MPa was applied for 30 seconds. The PET film on the low moisture permeability layer side of the resin sheet with the support was peeled off, and the low moisture permeability layer was placed on the organic EL element side on a substrate (horizontal: 25mm, vertical: 25 mm) having an organic EL element (light emitting area: about 4mm phi), and a roll laminator (manufactured by FUJIPLA, LPD2325, material of roll: rubber) was used under a nitrogen atmosphere at a roll temperature: 90 ℃, roller speed: 360 mm/min, roll press: laminating the resin sheet with the support under 0.2MPa to obtain an organic EL device in which the organic EL element is sealed with the resin sheet with the support;

A voltage was applied to the sealed organic EL element, and the initial light-emitting area before the sealing was measured in a constant humidity and constant temperature bath. Next, the organic EL device was stored in a constant humidity oven set to a temperature of 85 ℃ and a relative humidity of 85%. After the organic EL device was stored for 100 hours, the organic EL device was taken out from the constant humidity and constant temperature bath, a voltage was applied to the organic EL device, and the light-emitting area after the storage was measured;

as an index for comparing sealability (barrier property), the residual light-emitting area ratio was calculated from the following formula:

light-emitting area reduction ratio (%) =100× (dark spot area)/(initial light-emitting area)

Evaluation was performed according to the following criteria. The results are shown in Table 2;

(reference for reduction ratio of light-emitting area)

The light-emitting area reduction ratio was evaluated as o when 10% or less

The light-emitting area reduction ratio was evaluated as delta when it was 10% or more and less than 30%

The light-emitting area reduction rate was evaluated as 30% or more.

< Ca sealing Property measurement >)

The resin sheet was evaluated for sealability (barrier property) against moisture entering from the frame and the vertical direction using calcium. The alkali-free glass having a square of 50mm×50mm was washed with boiled isopropyl alcohol for 5 minutes, and dried at 150 ℃ for 30 minutes or more. After the washing, UV ozone washing was performed. Using this glass, calcium (purity 99.8%) was evaporated (thickness 200 nm) using a mask having a distance of 2mm from the end. The PET film on the hygroscopic layer side of the resin sheet with support produced in examples and comparative examples was peeled off, and the hygroscopic layer was bonded to PET film "je mueller 38R80" (PET: 35 μm: trade name manufactured by eastern vending company) to obtain another resin sheet with support. The PET film on the low moisture permeability layer side of the obtained resin sheet with a support was peeled off, and this low moisture permeability layer was bonded to an alkali-free glass on which calcium was deposited using a hot laminator (takida A4 (LPD 2325)) in a glove box to obtain a sample for evaluation. The sample for evaluation was stored at 25℃under a relative humidity of 40%, and after 24 hours, the state of calcium was visually observed. The case where calcium was visually confirmed was rated as "o", and the case where calcium adsorbed moisture, became calcium hydroxide, became transparent, and could not be visually confirmed was rated as "x". The results are shown in Table 2.

< Water vapor Transmission 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 PET film "je mueller 38R80" (PET: 35 μm: trade name manufactured by eastern vending company) as a support was laminated on the hygroscopic layer using a batch vacuum laminator (manufactured by Nichigo-Morton company, V-160), to obtain another resin sheet with a support. The lamination conditions were: pressurizing at 80deg.C for 30 seconds and under 0.3MPa for 30 seconds; the water vapor permeability of the resin sheet portion of the obtained resin sheet with the support was determined by an infrared sensor method according to JIS K7129B. Water vapor transmission rate (g/m) ² 24 hours) was measured using a water vapor permeability measuring apparatus (manufactured by film health (MOCON) Co., ltd., PERMATRAN-W3/34) at a temperature of 40℃under an atmosphere having a relative humidity of 90%;

the water vapor permeability of the resin sheet was calculated from:

1/P＝1/P1+1/P2

p: water vapor permeability of resin sheet with support

P1: water vapor transmission rate of resin sheet

P2: water vapor permeability of 35. Mu.m PET film (support) (15 g/m) ² 24 hours to calculate

The resin sheet portions of the resin sheets with the support manufactured in examples and comparative examples having different film thicknesses were compared by converting the film thickness into 50 μm by the following formula;

P3＝P1*X1/50

P3: water vapor transmission rate of resin sheet alone

X1: the resin sheet alone has a film thickness.

TABLE 2

As is clear from the results in table 2, the resin sheets with support of examples 1 to 5 exhibited good results in measurement of Ca sealing performance, and exhibited higher moisture barrier properties. Further, it was found that the organic EL elements sealed with the resin sheets with support of examples 1 to 5 exhibited high moisture barrier properties, and thus the light-emitting area reduction rate after 100 hours was low, and the device reliability was improved.

Industrial applicability

The present invention provides a resin sheet with a support for sealing, which exhibits higher moisture barrier properties and can improve the reliability of an organic EL element device.

The present application is based on Japanese patent application No. 2019-063225, the entire contents of which are incorporated herein.

Description of the reference numerals

1. Hygroscopic layer

2. A low moisture permeability layer.

Claims (20)

1. A resin sheet with a support, comprising 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

At least one low moisture permeability layer formed of the low moisture permeability resin composition,

at least one low moisture permeability layer is provided on the opposite side of the support from the moisture absorption layer,

the hygroscopic resin composition contains a hygroscopic filler,

the low moisture permeability resin composition comprises a platy filler,

the platy filler is at least one selected from platy glass, uncalcined hydrotalcite, smectite and synthetic fluorophlogopite.

2. The resin sheet with a support according to claim 1, wherein the content of the hygroscopic filler in the hygroscopic resin composition is 10 mass% or more and 80 mass% or less, assuming that the nonvolatile content of the hygroscopic resin composition is 100 mass%.

3. The resin sheet with a support according to claim 2, wherein the content of the hygroscopic filler in the hygroscopic resin composition is 20 mass% or more and 75 mass% or less, assuming that the nonvolatile content of the hygroscopic resin composition is 100 mass%.

4. The resin sheet with a support according to claim 1 or 2, wherein the content of the plate-like filler in the low moisture-permeable resin composition is 10 mass% or more and 80 mass% or less, assuming that the nonvolatile content of the low moisture-permeable resin composition is 100 mass%.

5. The resin sheet with a support according to claim 4, wherein the content of the plate-like filler in the low moisture-permeable resin composition is 30 mass% or more and 70 mass% or less, based on 100 mass% of the nonvolatile component of the low moisture-permeable resin composition.

6. The resin sheet with a support according to claim 1, wherein the hygroscopic filler is a semi-calcined hydrotalcite.

7. The resin sheet with a support according to claim 1, wherein an average particle diameter-thickness ratio of the plate-like filler is 2 or more.

8. The resin sheet with a support according to claim 7, wherein the average particle diameter-thickness ratio of the plate-like filler is 5 or more.

9. The resin sheet with a support according to claim 1, wherein the thickness of the resin sheet is 5 μm or more and 100 μm or less.

10. The resin sheet with a support according to claim 1, wherein the thickness of the hygroscopic layer is not less than the thickness of the low-moisture-permeability layer.

11. The resin sheet with a support according to claim 1, wherein a ratio of a thickness of the hygroscopic layer to a thickness of the low-moisture-permeability layer is 1.0 to 20.

12. The resin sheet with a support according to claim 1, wherein at least one layer of low moisture permeability is provided on the opposite side of the support to all the moisture absorption layers.

13. The resin sheet with a support according to claim 1, wherein the water vapor permeability of the resin sheet is 10 g/(m) ² 24 hours) or less.

14. The resin sheet with a support according to claim 13, wherein the water vapor permeability of the resin sheet is 5 g/(m) ² 24 hours) or less.

15. The resin sheet with a support according to claim 1, wherein the hygroscopic resin composition and the low moisture permeability resin composition contain thermosetting resins.

16. The resin sheet with a support according to claim 1, wherein the hygroscopic resin composition and the low moisture permeability resin composition contain an epoxy resin.

17. The resin sheet with a support according to claim 1, wherein the hygroscopic resin composition and the low moisture permeability resin composition contain a thermoplastic resin.

18. The resin sheet with a support according to claim 1, which is used for sealing an electronic device.

19. The resin sheet with a support according to claim 1, which is used for sealing an organic EL device.

20. An electronic device sealed with the support-carrying resin sheet according to claim 1.

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