JP2020158739A - Resin composition and resin sheet - Google Patents

Abstract

To provide a resin composition that can exhibit a higher moisture shielding property, and is suitable for forming an encapsulation part of a light-emitting element such as an organic EL element, an optical semiconductor such as a high-brightness LED, and a light receiving element or the like such as a solar cell.SOLUTION: A resin composition, containing the following components (A) to (C): (A) thermoplastic resin; (B) hygroscopic filler; and (C) plate-like filler, and having a water content of 1500 ppm or less.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and a resin sheet, and is a resin composition suitable for encapsulating electronic elements, particularly light emitting elements such as organic EL (Electroluminescence) elements, optical semiconductors such as high-brightness LEDs, and light receiving elements such as solar cells. And regarding resin sheets.

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 to provide a resin composition and a resin sheet suitable for sealing capable of exhibiting higher moisture shielding properties. That is.

As a result of diligent research to solve the above problems, the present inventors have solved the above problems by blending a hygroscopic filler and a plate-like filler with a thermoplastic resin and setting the water content within a predetermined range. This has led to the completion of the present invention. That is, the present invention includes those having the following characteristics.
[1] The following components (A) to (C):
(A) Thermoplastic resin;
A resin composition containing (B) a hygroscopic filler; and (C) a plate-like filler and having a water content of 1500 ppm or less.
[2] The resin composition according to [1], wherein the (A) thermoplastic resin is a polyolefin resin.
[3] The resin composition according to [1] or [2], wherein the content of the hygroscopic filler (B) is 10% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition. ..
[4] The method according to any one of [1] to [3], wherein the content of the plate-shaped filler (C) is 10% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition. Resin composition.
[5] Any of [1] to [4], wherein the mass ratio of (B) hygroscopic filler to (C) plate-shaped filler (hygroscopic filler: plate-shaped filler) is 10: 1 to 1: 5. The resin composition described in Crab.
[6] The resin composition according to any one of [1] to [5], wherein the hygroscopic filler is semi-calcined hydrotalcite.
[7] The resin according to any one of [1] to [6], wherein the plate-shaped filler is at least one selected from plate-shaped glass, uncalcined hydrotalcite, smectite, and synthetic phlogopite. Composition.
[8] (C) The resin composition according to any one of [1] to [7], wherein the plate-shaped filler has an average aspect ratio of 2 or more.
[9] A resin sheet having a support and a resin composition layer containing the resin composition according to any one of [1] to [8] provided on the support.
[10] The resin sheet according to [9], which is used for sealing an electronic device.
[11] The resin sheet according to [9], which is used for sealing an organic EL device.
[12] An electronic device sealed with the resin sheet according to [9].
[13] An organic EL device sealed with the resin sheet according to [9].

According to the present invention, a resin composition capable of exhibiting higher moisture shielding properties and suitable for sealing light emitting elements such as organic EL elements, optical semiconductors such as high-brightness LEDs, and light receiving elements such as solar cells, and A resin sheet can be provided.

Hereinafter, the present invention will be described according to its preferred embodiment.
[Resin composition]
The resin composition of the present invention contains (A) a thermoplastic resin, (B) a hygroscopic filler and (C) a plate-like filler as essential components, and has a water content of 1500 ppm or less.

<(A) Thermoplastic resin>
The thermoplastic resin used in the present invention (hereinafter, also referred to as component (A)) can be used without particular limitation, and for example, a polyolefin resin, a polyester resin, a cycloolefin resin, a phenoxy resin, a polyvinyl acetal resin, and a polyimide. Examples thereof include resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, (meth) acrylic resins and the like. Among these, polyolefin-based resins are preferable in terms of adhesiveness and adhesive wet heat resistance. Only one type of these thermoplastic resins may be used, or two or more types may be used in combination.

(Polyolefin resin)
The polyolefin-based resin that can be used in the present invention is not particularly limited as long as it has a skeleton derived from an olefin monomer. For example, the polyolefin-based resins described in Patent Documents 1 and 2 are known. As the polyolefin-based resin, a polyethylene-based resin, a polypropylene resin, a polybutene resin, and a polyisobutylene resin are preferable. These polyolefin-based resins may be homopolymers, or copolymers such as random copolymers and block copolymers. Examples of the copolymer include a copolymer of two or more kinds of olefins and a copolymer of the olefin and a monomer other than the olefin such as unconjugated diene and styrene. Examples of preferred copolymers are ethylene-non-conjugated diene copolymers, ethylene-propylene copolymers, ethylene-propylene-non-conjugated diene copolymers, ethylene-butene copolymers, propylene-butene copolymers, propylene. Examples thereof include a-butene-non-conjugated diene copolymer, a styrene-isobutylene copolymer, and a styrene-isobutylene-styrene copolymer. As the polyolefin-based resin, for example, the isobutylene-modified resin described in International Publication No. 2011/62167, the styrene-isobutylene-modified resin described in International Publication No. 2013/108731, and the like are preferably used.

The polyolefin-based resin is a polyolefin-based resin having an acid anhydride group (that is, a carbonyloxycarbonyl group (-CO-O-CO-)) and / / from the viewpoint of imparting excellent physical properties such as adhesiveness and adhesive wet heat resistance. Alternatively, it preferably contains a polyolefin-based resin having an epoxy group. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride and the like. The acid anhydride group can have one kind or two or more kinds. The polyolefin-based resin having an acid anhydride group is, for example, an unsaturated compound having an acid anhydride group, and is obtained by graft-modifying the polyolefin resin under radical reaction conditions. Further, an unsaturated compound having an acid anhydride group may be radically copolymerized together with an olefin or the like. Similarly, the polyolefin-based resin having an epoxy group is an unsaturated compound having an epoxy group such as glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether, and the polyolefin-based resin is subjected to radical reaction conditions. It is obtained by graft modification with. Further, an unsaturated compound having an epoxy group may be radically copolymerized together with an olefin or the like. One type or two or more types of polyolefin-based resin can be used, and a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group may be used in combination.

The concentration of the acid anhydride group in the polyolefin-based resin having an acid anhydride group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The concentration of the acid anhydride group is obtained from the value of the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of the resin according to the description of JIS K 2501. The amount of the polyolefin-based resin having an acid anhydride group in the polyolefin-based resin is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.

The concentration of the epoxy group in the polyolefin resin having an epoxy group is preferably 0.05 to 10 mmol / g, more preferably 0.1 to 5 mmol / g. The epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995. The amount of the polyolefin-based resin having an epoxy group in the polyolefin-based resin is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.

From the viewpoint of imparting excellent physical properties such as moisture permeability, the polyolefin-based resin preferably contains both a polyolefin-based resin having an acid anhydride group and a polyolefin-based resin having an epoxy group. In such a polyolefin resin, an acid anhydride group and an epoxy group are reacted by heating to form a crosslinked structure, and a sealing layer having excellent moisture permeation resistance and the like can be formed. The crosslinked structure can be formed after sealing, but when the object to be sealed is heat-sensitive, such as an organic EL element, it is sealed using a sealing film, and when the sealing film is manufactured. It is desirable to form a crosslinked structure. The ratio of the polyolefin resin having an acid anhydride group to the polyolefin resin having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed, but the molar ratio of the epoxy group to the acid anhydride group (epoxide group: acid anhydride). The group) is preferably 100: 10 to 100: 200, more preferably 100: 50 to 100: 150, and particularly preferably 100: 90 to 100: 110.

The number average molecular weight of the polyolefin-based resin is not particularly limited, but from the viewpoint of providing good coatability of the varnish of the resin composition and good compatibility with other components in the resin composition, 1,000, 000 or less is preferable, 750,000 or less is more preferable, 500,000 or less is further preferable, 400,000 or less is further preferable, 300,000 or less is further preferable, 200,000 or less is particularly preferable, and 150,000 or less is particularly preferable. The following are the most preferable. On the other hand, from the viewpoint of preventing repelling during coating of the varnish of the resin composition, developing the moisture permeability of the formed resin composition layer, and improving the mechanical strength, this number average molecular weight is 1,000. The above is preferable, 3,000 or more is more preferable, 5,000 or more is further preferable, 10,000 or more is further preferable, 30,000 or more is further preferable, and 50,000 or more is particularly preferable. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is measured by moving LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Co., Ltd. as a column. It can be measured using toluene or the like as a phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

The polyolefin-based resin in the present invention is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish. Here, amorphous means that the polyolefin resin does not have a clear melting point, and for example, when the melting point is measured by DSC (differential scanning calorimetry) of the polyolefin resin, no clear peak is observed. You can use things.

Next, a specific example of the polyolefin resin will be described. Specific examples of the polyisobutylene resin include "Opanol B100" manufactured by BASF (viscosity average molecular weight: 1,110,000) and "B50SF" manufactured by BASF (viscosity average molecular weight: 400,000).

Specific examples of the polybutene resin include "HV-1900" (polybutene, number average molecular weight: 2,900) manufactured by JX Energy Co., Ltd. and "HV-300M" (maleic anhydride-modified liquid polybutene) manufactured by Toho Chemical Industry Co., Ltd. ("HV"). -300 ”(modified product with number average molecular weight: 1,400), number average molecular weight: 2,100, number of carboxy groups constituting the acid anhydride group: 3.2 / 1 molecule, acid value: 43. 4 mgKOH / g, acid anhydride group concentration: 0.77 mmol / g).

Specific examples of the styrene-isobutylene copolymer include "SIBSTAR T102" manufactured by Kaneka (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Seikou PMC. "T-YP757B" (maleic anhydride-modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 100,000), "T-YP766" manufactured by Seikou PMC. (Glysidyl methacrylate-modified styrene-isobutylene-styrene block copolymer, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 100,000), "T-YP8920" manufactured by Seikou PMC (maleic anhydride-modified styrene-isobutylene anhydride) -Styrene copolymer, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,800), "T-YP8930" manufactured by Seikou PMC (glycidyl methacrylate-modified styrene-isobutylene-styrene copolymer, epoxy Group concentration: 0.638 mmol / g, number average molecular weight: 48,700).

Specific examples of the polyethylene-based resin or polypropylene-based resin include "EPT X-3012P" manufactured by Mitsui Chemicals, Inc. (ethylene-propylene-5-ethylidene-2-norbornene copolymer, "EPT1070" manufactured by Mitsui Chemicals, Inc. (ethylene-propylene). -Dicyclopentadiene copolymer), "Toughmer A4085" (ethylene-butene copolymer) manufactured by Mitsui Chemicals, Inc. can be mentioned.

As a specific example of the propylene-butene-based copolymer, "T-YP341" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene unit per 100% by mass of propylene unit and butene unit in total). : 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), "T-YP279" manufactured by Seikou PMC (maleic anhydride-modified propylene-butene random copolymer, propylene unit and butene) Amount of butene unit per 100% by mass of total units: 36% by mass, acid anhydride group concentration: 0.464 mmol / g, number average molecular weight: 35,000), "T-YP276" (glycidyl methacrylate) manufactured by Seikou PMC. Modified propylene-butene random copolymer, amount of butene unit per 100% by mass of propylene unit and butene unit: 36% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 57,000), starlight "T-YP312" manufactured by PMC (maleic anhydride-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units in total: 29% by mass, acid anhydride group concentration: 0. 464 mmol / g, number average molecular weight: 60,900), "T-YP313" manufactured by Seikou PMC (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units in total) : 29% by mass, epoxy group concentration: 0.638 mmol / g, number average molecular weight: 155,000), "T-YP429" manufactured by Seikou PMC (maleic anhydride-modified ethylene-methyl methacrylate copolymer, ethylene unit and methyl) Amount of methyl methacrylate unit per 100% by mass of total methacrylate unit: 32% by mass, acid anhydride group concentration: 0.46 mmol / g, number average molecular weight: 2,300), Seikou PMC "T-YP430" ( Maleic anhydride-modified ethylene-methylmethacrylate copolymer, amount of methylmethacrylate units per 100% by mass of ethylene units and methylmethacrylate units: 32% by mass, acid anhydride group concentration: 1.18 mmol / g, number average molecular weight : 4,500), "T-YP431" manufactured by Starlight PMC (glycidyl methacrylate-modified ethylene-methylmethacrylate copolymer, epoxy group concentration: 0.64 mmol / g, number average molecular weight: 2,400), manufactured by Starlight PMC. "T-YP432" ( Glysidyl methacrylate-modified ethylene-methyl methacrylate copolymer, epoxy group concentration: 1.63 mmol / g, number average molecular weight: 3,100) can be mentioned.

The content of the component (A) in the resin composition of the present invention is not particularly limited. However, from the viewpoint of providing good coatability and compatibility, and ensuring good moist heat resistance and handleability (tack suppression), the content is 80% by mass with respect to 100% by mass of the non-volatile content of the resin composition. % Or less is preferable, 75% by mass or less is more preferable, 70% by mass or less is further preferable, 60% by mass or less is further preferable, 55% by mass or less is further preferable, and 50% by mass or less is particularly preferable. On the other hand, from the viewpoint of improving moisture permeation resistance and transparency, the content is preferably 1% by mass or more, more preferably 3% by mass or more, based on 100% by mass of the non-volatile content in the resin composition. 5, 5% by mass or more is further preferable, 7% by mass or more is further preferable, 10% by mass or more is further preferable, 35% by mass or more is particularly preferable, and 40% by mass or more is most preferable.

<(B) Hygroscopic filler>
The hygroscopic filler used in the present invention (hereinafter, also referred to as component (B)) is not particularly limited as long as it is a filler having hygroscopicity, and is, for example, calcium oxide, magnesium oxide, calcined hydrotalcite, or the like. Examples thereof include metal oxides and layered metal hydroxides such as semi-baked hydrotalcite. 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 plate-shaped filler suppresses the arrival of the trapped moisture to the organic EL element. Therefore, by fully utilizing the hygroscopicity of the semi-baked hydrotalcite, a particularly preferable resin composition can be obtained from the viewpoint of moisture shielding property. 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 component (B) in the resin composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10% by mass with respect to 100% by mass of the non-volatile content of the resin composition. % Or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, and even more preferably 20% by mass or more and 70% by mass or less. When the content of the component (B) is 10% by mass or more, the hygroscopic performance can be exhibited more effectively. Further, by setting the content of the component (B) 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.

<(C) Plate-shaped filler>
The plate-shaped filler (hereinafter, also referred to as (C) component) used in the present invention is plate-shaped, and is not particularly limited as long as the effects of the present invention are exhibited, but the (C) plate in the present invention. The state filler does not contain (B) a hygroscopic filler. That is, the plate-shaped filler (C) 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 (C) 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, uncalcined hydrotalcite, smectite and synthetic phlogopite are preferable because they have a high aspect ratio, exhibit moisture blocking property, 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 component (C) in the resin composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10% by mass with respect to 100% by mass of the non-volatile content of the resin composition. % 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 component (C) to 10% by mass or more, the effect of water blocking property can be more effectively exhibited. Further, by setting the content of the component (C) 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 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, still more preferably 0.2 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 mass ratio of the hygroscopic filler to the plate-shaped filler in the resin composition of the present invention (hygroscopic filler: plate-shaped filler) is not particularly limited as long as the effect of the present invention is exhibited, but it has a high moisture shielding property. From the viewpoint of sex, it is preferably 10: 1 to 1: 5, more preferably 8: 1 to 1: 4, and even more preferably 5: 1 to 1: 2.5.

The resin composition of the present invention may contain a filler other than the hygroscopic filler and the plate-shaped filler as long as the effects of the present invention are not impaired. Examples of fillers other than the hygroscopic filler and the plate-shaped filler include silica, alumina, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, and strontium titanate. , Calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium zirconate, calcium zirconate, inorganic fillers such as silicate, rubber particles, silicone powder, nylon powder, organic fillers such as fluororesin powder Examples include fillers. The content of the filler other than the hygroscopic filler and the plate-shaped filler is preferably 50% by mass or less, more preferably 30% by mass or less, when the total amount of the hygroscopic filler and the plate-shaped filler is 100% by mass. , More preferably 20% by mass or less, and even more preferably 10% by mass or less.

<(D) Adhesive agent>
The resin composition of the present invention may further contain a tackifier (hereinafter, also referred to as component (D)). The tackifier is also called a tack fire, and is a resin that is blended with a plastic polymer to impart tackiness. The tackifier is not particularly limited, and is terpene resin, modified terpene resin (hydrogenated terpene resin, terpene phenol copolymer resin, aromatic modified terpene resin, etc.), kumaron resin, indene resin, petroleum resin (fat). Group petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins and their hydrides, etc.) are preferable. used.

Examples of commercially available products that can be used as a tackifier include the following. Examples of the terpene resin include YS resin PX and YS resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.), and examples of the aromatic-modified terpene resin include YS resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.). Examples of the terpene resin include Clearon P, Clearon M, and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and examples of the terpene phenol copolymer resin include YS Polystar 2000, Polystar U, Polystar T, Polystar S, and Mighty Ace G (all of which are manufactured by Yasuhara Chemical Co., Ltd.). Yasuhara Chemical Co., Ltd.), etc., Escorez 5300 series, 5600 series (both manufactured by Exxon Mobile Co., Ltd.), etc. as hydrogenated alicyclic petroleum resins, and ENDEX155 (manufactured by Eastman Co., Ltd.) as aromatic petroleum resins. Etc., as an aliphatic aromatic copolymerized petroleum resin, Quintone D100 (manufactured by Nippon Zeon Co., Ltd.) and the like, and as an alicyclic petroleum resin, Quintone 1325, Quintone 1345 (both manufactured by Nippon Zeon Co., Ltd.) and the like. Examples of the saturated hydrocarbon resin include Archon P100, Archon P125, Archon P140, and TFS13-030 (all manufactured by Arakawa Chemical Co., Ltd.).

The softening point of the tackifier is preferably 50 to 200 ° C, more preferably 90 to 180 ° C, and 100 to 150 from the viewpoint that the sheet is softened in the laminating step of the resin composition sheet and has desired heat resistance. ℃ is more preferable. The softening point is measured by the ring-and-ball method according to JIS K2207.

The tackifier may be used alone or in combination of two or more. The content of the tackifier in the resin composition is not particularly limited. However, from the viewpoint of maintaining good moisture permeation resistance of the resin composition, when a tackifier is used, the content thereof is preferably 80% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition. It is more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less. On the other hand, from the viewpoint of having sufficient adhesiveness, when a tackifier is used, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the non-volatile content of the resin composition. It is preferable, and more preferably 15% by mass or more.

Of these, petroleum resins are preferable from the viewpoints of adhesiveness, moisture permeability resistance, transparency and the like of the resin composition. Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins. Of these, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferable from the viewpoints of adhesiveness, moisture permeability resistance, compatibility, and the like of the resin composition. Further, from the viewpoint of improving transparency, an alicyclic petroleum resin is particularly preferable. As the alicyclic petroleum resin, one obtained by hydrogenating an aromatic petroleum resin can also be used. In this case, the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, still more preferably 50 to 90%. If the hydrogenation rate is too low, there is a tendency for the transparency to decrease due to coloring, and if the hydrogenation rate is too high, the production cost tends to increase. The hydrogenation rate can be obtained from the ratio of the peak intensities of ¹ H-NMR of hydrogen in the aromatic ring before and after hydrogenation. As the alicyclic petroleum resin, a cyclohexane ring-containing hydrogenated petroleum resin and a dicyclopentadiene hydrogenated petroleum resin are particularly preferable. The petroleum resin may be used alone or in combination of two or more. The number average molecular weight Mn of the petroleum resin is preferably 100 to 2,000, more preferably 700 to 1,500, and even more preferably 500 to 1,000.

<(E) Hardener>
The resin composition of the present invention may further contain a curing agent (hereinafter, also referred to as component (E)) from the viewpoint of improving the curing performance of the resin composition. The curing agent is not particularly limited, and examples thereof include an amine-based curing agent, a guanidine-based curing agent, an imidazole-based curing agent, a phosphonium-based curing agent, and a phenol-based curing agent. The curing agent may be used alone or in combination of two or more.

The amine-based curing agent is not particularly limited, but is a quaternary ammonium salt such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1,8-diazabicyclo [5.4.0] undecene-7), DBN ( 1,5-Diazabicyclo [4.3.0] nonen-5), DBU-phenol salt, DBU-octylate, DBU-p-toluenesulfonate, DBU-gerate, DBU-phenol novolac resin salt, etc. Diazabicyclo compound; tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol (TAP) and their salts, aromatic dimethylurea, aliphatic dimethylurea. , Dizabiurea compounds such as aromatic dimethylurea; and the like. These may be used alone or in combination of two or more.

The guanidine-based curing agent is not particularly limited, but is not particularly limited, but is a dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4] .0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexyl Biguanides, 1-allyl biguanides, 1-phenylbiguanides, 1- (o-tolyl) biguanides and the like can be mentioned. These may be used alone or in combination of two or more.

The imidazole-based curing agent is not particularly limited, but 1H-imidazole, 2-methyl-imidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl-imidazole, 2-phenyl-4. , 5-Bis (hydroxymethyl) -imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 2-dodecyl-imidazole, Examples thereof include 2-heptadecylimidazole and 1,2-dimethyl-imidazole. These may be used alone or in combination of two or more.

The phosphonium-based curing agent is not particularly limited, but is triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) tri. Examples thereof include phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. These may be used alone or in combination of two or more.

The type of phenol-based curing agent is not particularly limited, but triazine skeleton-containing phenol-based curing agent, triazine skeleton-containing phenol novolac curing agent, MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), NHN, Examples thereof include CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Kayaku Corporation), TD2090 (manufactured by DIC Corporation) and the like. Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018 (manufactured by DIC Corporation) and the like. Specific examples of the triazine skeleton-containing phenol novolac curing agent include LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like. These may be used alone or in combination of two or more.

The content of the curing agent in the resin composition of the present invention is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when a curing agent is used, the content thereof is preferably 5% by mass or less, preferably 1% by mass or less, based on 100% by mass of the non-volatile content of the resin composition. More preferred. On the other hand, from the viewpoint of suppressing tack, when a curing agent is used, the content thereof is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on 100% by mass of the non-volatile content of the resin composition. More preferred.

<(F) Resin having a functional group capable of reacting with an epoxy group>
When a polyolefin resin having an epoxy group as the component (A) is used in the resin composition of the present invention, a functional group capable of reacting with the (F) epoxy group as a component for forming a crosslinked structure with the component (A). It is desirable to use a resin having (hereinafter sometimes abbreviated as "component (F)"). Examples of the functional group capable of reacting with the epoxy group include a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group, an acid anhydride group and the like, and an acid anhydride group is preferable. Examples of the acid anhydride group include a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride and the like. Examples of the resin include polyolefin resins (excluding polyolefin resins having an acid anhydride group as component (A)), acrylic resins, melamine resins, phenol resins, urea resins, polyester resins, alkyd resins, polyurethanes, and polyimides. Examples thereof include resins, and polyolefin resins are preferable. The polyolefin-based resin as the component (F) is the same as the component (A) described above except that it has a hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxy group and the like as a functional group instead of an acid anhydride group. Polyolefin-based resins can be mentioned, with polybutene being preferred.

The content of the component (F) in the resin composition of the present invention is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeation resistance, when the component (F) is used, the content thereof is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the non-volatile content of the resin composition. The following is more preferable. On the other hand, when the component (F) is used from the viewpoint of suppressing tack, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the non-volatile content of the resin composition. ..

<Resin having a functional group capable of reacting with (G) acid anhydride group>
When a polyolefin resin having an acid anhydride group is used as the component (A) in the resin composition of the present invention, it reacts with the (G) acid anhydride group as a component for forming a crosslinked structure with the component (A). It is desirable to use a resin having a possible functional group (hereinafter, may be abbreviated as "component (G)"). Examples of the functional group capable of reacting with the acid anhydride group include a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group and the like, and an epoxy group is preferable. Examples of the resin include polyolefin resins (excluding polyolefin resins having an epoxy group as component (A)), acrylic resins, melamine resins, phenol resins, urea resins, polyester resins, alkyd resins, polyurethanes, and polyimide resins. However, a polyolefin resin is preferable. The polyolefin resin as the component (G) is described above except that it has a hydroxyl group, a primary or secondary amino group, a thiol group, an epoxy group, an oxetane group and the like as a functional group instead of an epoxy group. A) Examples thereof include a polyolefin resin similar to the component, and polybutene is preferable.

The content of the component (G) in the resin composition of the present invention is not particularly limited. However, from the viewpoint of preventing a decrease in moisture permeability, when the component (G) is used, the content thereof is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the non-volatile content of the resin composition. The following is more preferable. On the other hand, from the viewpoint of suppressing tack, when the component (G) is used, the content thereof is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the non-volatile content of the resin composition. ..

<(H) Plasticizer>
The resin composition of the present invention may further contain a (H) plasticizer (hereinafter, may be abbreviated as "(H) component"). By using the component (H), the flexibility and moldability of the resin composition can be improved. The component (H) is not particularly limited, but a material liquid at room temperature is preferably used. Specific examples of the plasticizer include paraffin-based process oil, naphthen-based process oil, liquid paraffin, polyethylene wax, polypropylene wax, mineral oil such as vaseline, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, palm oil, and olive oil. Examples thereof include vegetable oils such as, liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and liquid poly α-olefins such as hydrogenated liquid polybutadiene. As the plasticizer used in the present invention, liquid poly-α-olefins are preferable, and liquid polybutadiene is particularly preferable. The liquid poly-α-olefin preferably has a low molecular weight from the viewpoint of adhesiveness, and preferably has a weight average molecular weight in the range of 500 to 5,000, more preferably 1,000 to 3,000. One of these plasticizers may be used alone, or two or more of these plasticizers may be used in combination. Here, "liquid" is a state of the plasticizing agent at room temperature (25 ° C.). When the component (H) is used, the content thereof is preferably 50% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition from the viewpoint of not adversely affecting the organic EL element.

<Other additives>
The resin composition of the present invention may optionally contain various additives other than the above-mentioned components to the extent that the effects of the present invention are not impaired. Examples of such additives include resins other than the above-mentioned components (A), (F) and (G) (for example, epoxy resin, urethane resin, acrylic resin, polyamide resin, etc.); Orben, Benton, etc. Thickeners; silicone-based, fluorine-based, polymer-based defoaming agents or leveling agents; adhesion-imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; and the like.

<Moisture content>
The resin composition of the present invention has a water content of 1500 ppm or less. The water content is preferably 1450 ppm or less, more preferably 1400 ppm or less. If the water content exceeds 1500 ppm, it becomes difficult to exhibit high water shielding properties. The water content can be calculated according to the method described in the following examples.

<Pressure-sensitive adhesive>
The resin composition of the present invention is preferably a pressure-sensitive adhesive. The pressure-sensitive adhesive means an adhesive that adheres only by applying pressure at room temperature for a relatively short time, and is well known to those skilled in the art. Further, the resin composition of the present invention is more preferably a pressure-sensitive adhesive containing (D) a tackifier and having adhesiveness.

<Manufacturing method of resin composition>
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is added with a solvent or the like, if necessary, and mixed using a kneading roller, a rotary mixer, or the like.

<Use>
The resin composition of the present invention can be used as a transparent member for a light transmitting portion or a light extracting portion of an optical semiconductor device having a light emitting element or a light receiving element such as an EL element (organic or inorganic), a high-brightness LED element, or a solar cell. used. For example, the film-like cured product obtained from the resin composition of the present invention can be used as it is as a transparent panel or the like for forming a light transmitting portion or a light extracting portion. Generally, the term "panel" is used for products with relatively high hardness (rigidity), and the terms "film" and "sheet" tend to be used for products with relatively low hardness (rigidity). , "Panel" here also means a product with relatively high hardness (rigidity).

When the resin composition of the present invention is formed into a film, for example, a varnish (resin composition varnish) prepared by mixing the components of the resin composition and an organic solvent using a kneading roller, a rotary mixer, or the like is used. The organic solvent is removed from the varnish applied on the support by heating (hot air blowing, etc.) and / or decompression treatment using a known device after applying it on the release-treated support to form a film. A molded resin composition is obtained (hereinafter, also referred to as "film-like resin composition").

Examples of the support of the release-treated support include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; cycloolefin polymers; polyethylene terephthalate (hereinafter, may be abbreviated as “PET”), polyethylene naphthalate, and the like. Polyester; Polypropylene; Plastic films such as polyimide (preferably PET film) and metal foils such as aluminum foil, stainless steel foil, and copper foil are used. Examples of the mold release treatment of the support that has been released include a mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, and a fluororesin-based mold release agent.

The solid content of the resin composition varnish is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.

The heating conditions for removing the organic solvent from the resin composition varnish are not particularly limited, but usually about 2 to 10 minutes at about 50 to 130 ° C. is preferable.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and cellosolves such as cellosolve. Examples thereof include carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Only one of these organic solvents may be used, or two or more of them may be used in combination.

The thickness of the film-shaped resin composition varies depending on the apparatus to which the film-shaped resin composition is applied and the application location, but is preferably in the range of 1 to 1000 μm, more preferably 2 to 800 μm.

The film-like resin composition formed on the support is preferably protected by a protective film for protection until the resin composition is cured. For example, the film-like resin composition formed on the support. A protective film that has been subjected to a mold release treatment can be laminated on the resin composition of the above by using a known device. Examples of the equipment used for laminating the protective film include a roll laminator, a press machine, a vacuum pressurizing laminator, and the like.

The release-treated protective film is, for example, a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride; a cycloolefin polymer; a polyester such as polyethylene terephthalate (hereinafter, may be abbreviated as “PET”), a polyester such as polyethylene naphthalate; a polycarbonate; A plastic film (preferably PET film) such as polyimide, or a support made of a metal foil such as aluminum foil, stainless steel foil, or copper foil, which has been subjected to a mold release treatment, is used. Examples of the mold release treatment include a mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, and a fluororesin-based mold release agent.

<Resin sheet>
The resin sheet of the present invention has a support and a resin composition layer containing the resin composition of the present invention provided on the support.

<Electronic device>
The electronic device in which the electronic element is sealed with the resin sheet of the present invention can be manufactured, for example, by laminating the resin sheet of the present invention on the electronic element on the 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, "parts" and "%" in the amount of a component and a copolymerization unit mean "parts by mass" and "% by mass", respectively, unless otherwise specified.
The materials used in Examples and Comparative Examples are shown below.

(A) Component "HV-1900" (manufactured by JX Energy Co., Ltd.): Polybutene, number average molecular weight 2,900
"HV-300M" (manufactured by Toho Chemical Industry Co., Ltd.): Maleic anhydride-modified liquid polybutene, acid anhydride group concentration 0.77 mmol / g, number average molecular weight 2,100
"T-YP341" (manufactured by Seiko PMC Corporation): glycidyl methacrylate-modified propylene-butene random copolymer (swazole solution, solid content 20%), propylene unit / butene unit 71% / 29%, epoxy group concentration 0.638 mmol / g, number average molecular weight 155,000
(B) Ingredient "DHT-4C" (manufactured by Kyowa Chemical Co., Ltd.): Semi-calcined hydrotalcite, average particle diameter 400 nm, BET specific surface area 15 m ² / g
(C) Component "PDM-5B" (manufactured by Topy Industries, Ltd.): Synthetic fluorine phlogopite, average particle diameter 5 μm, average aspect ratio 40
"FTD010-F01" (manufactured by Nippon Sheet Glass Co., Ltd.): Plate-shaped glass filler, average particle diameter 10 μm, average aspect ratio 25
(D) Component "Arcon P125" (manufactured by Arakawa Chemical Co., Ltd.): Cyclohexane ring-containing saturated hydrocarbon resin, softening point 125 ° C.
(E) Ingredients 2,4,6-tris (diaminomethyl) phenol (hereinafter abbreviated as "TAP") (manufactured by Kayaku Akzo Corporation): Amine-based curing agent

<Example 1>
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, manufactured by Arakawa Chemical Co., Ltd.) dissolved in swazole so as to have a solid content of 60%, and maleic anhydride-modified liquid polybutene (HV-300M, Toho Chemical Co., Ltd.) (Manufactured by Topy Industries), Polybutene (HV-1900, manufactured by JX Energy), semi-baked hydrocarbonite (hygroscopic filler; DHT-4C, manufactured by Kyowa Chemical Co., Ltd.) and synthetic phlogopite (plate-shaped filler; PDM-5B, (Manufactured by Topy Industries, Ltd.) was dispersed in three rolls to obtain a mixture. In the obtained mixture, a glycidyl methacrylate-modified propylene-butene random copolymer (T-YP341, manufactured by Seiko PMC, swazole solution, solid content 20%), an amine-based curing agent (TAP, manufactured by Kayaku Akzo) and toluene Was compounded, and the obtained mixture was uniformly dispersed with a high-speed rotary mixer to obtain a varnish of a resin composition. The obtained varnish was uniformly applied with a die coater on the mold release 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, and 130 A resin sheet having a resin composition layer having a thickness of 25 μm was obtained by heating at ° C. for 30 minutes, and then dried at 150 ° C. for 24 hours.

<Example 2>
The same method as in Example 1 except that a plate-shaped glass filler (FTD010-F01, manufactured by Nippon Sheet Glass Co., Ltd.) was used instead of the synthetic fluorine phlogopite (plate-shaped filler; PDM-5B, manufactured by Topy Industries, Ltd.). , A varnish of a resin composition and a resin sheet were prepared.

<Example 3>
The varnish and resin of the resin composition were prepared in the same manner as in Example 1 except that the amount of synthetic fluorine phlogopite (plate-shaped filler; PDM-5B, manufactured by Topy Industries, Ltd.) was changed from 100 parts to 50 parts. A sheet was prepared.

<Example 4>
The varnish and resin of the resin composition were prepared in the same manner as in Example 1 except that the amount of synthetic fluorine phlogopite (plate-shaped filler; PDM-5B, manufactured by Topy Industries, Ltd.) was changed from 100 parts to 150 parts. A sheet was prepared.

<Comparative example 1>
Varnishes having the compounding ratios shown in Table 1 below were prepared by the following procedure. Maleic anhydride-modified liquid polybutene (HV-300M, manufactured by Toho Kagaku Kogyo Co., Ltd.) in which a cyclohexane ring-containing saturated hydrocarbon resin (tackiness imparting agent; Archon P125) is dissolved in swazole so as to have a solid content of 60%. Polybutene (HV-1900, manufactured by JX Energy Co., Ltd.) 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 propylene-butene random copolymer (T-YP341, manufactured by Seikou 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 resin composition. The obtained varnish was uniformly applied with a die coater on the mold release 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, and 130 A resin sheet having a resin composition layer having a thickness of 25 μm was obtained by heating at ° C. for 30 minutes, and then dried at 150 ° C. for 24 hours.

<Comparative example 2>
Comparative Example 1 except that synthetic phlogopite (plate-shaped filler; PDM-5B, manufactured by Topy Industries, Ltd.) was used instead of semi-baked hydrotalcite (hygroscopic filler; DHT-4C, manufactured by Kyowa Chemical Co., Ltd.). A varnish and a resin sheet of the resin composition were prepared by the same method.

<Comparative example 3>
The method is the same as in Comparative Example 1 except that a plate-shaped glass filler (FTD010-F01, manufactured by Nippon Sheet Glass Co., Ltd.) is used instead of the semi-baked hydrotalcite (hygroscopic filler; DHT-4C, manufactured by Kyowa Chemical Co., Ltd.). To prepare a varnish and a resin sheet of the resin composition.

<Comparative example 4>
A varnish and a resin sheet of the resin composition were prepared by the same method as in Example 1 except that the drying was not performed at 150 ° C. for 24 hours.

<Comparative example 5>
A varnish and a resin sheet of the resin composition were prepared by the same method as in Example 2 except that the resin was not dried at 150 ° C. for 24 hours.

<Comparative Example 6>
A varnish and a resin sheet of the resin composition were prepared by the same method as in Example 1 except that the resin was dried at 150 ° C. for 1 hour instead of drying at 150 ° C. for 24 hours.

<Evaluation of total light transmittance>
The resin sheets produced in Examples and Comparative Examples were cut to a length of 50 mm and a width of 20 mm, and the cut resin sheets were cut into glass plates (length 76 mm, width 26 mm and thickness 1.2 mm microslide glass (Matsunami Glass Industry Co., Ltd.). The white slide glass S1112 edge polishing No. 2) was laminated using a batch type vacuum laminator (Nichigo Morton, V-160). The laminating conditions were a temperature of 80 ° C., a depressurization time of 30 seconds, and a pressure of 0. The pressure was applied at 3 MPa for 30 seconds. After that, the PET film of the resin sheet was peeled off, and the light transmission spectrum of the exposed and cured resin composition layer was measured with a φ80 mm integrating sphere (model name SRS-99-010, Measured using a fiber type spectrophotometer (MCPD-7700, type 311C, manufactured by Otsuka Electronics Co., Ltd., external light source unit: halogen lamp MC-2564 (24V, 150W specification)) equipped with a reflectance of 99%), and a wavelength of 450 nm. The total light transmittance (%) was calculated and evaluated according to the following criteria. The distance between the integrating sphere and the sample (laminated body) was 0 mm, and glass was used as a reference.
Good (○): 90% or more Bad (×): Less than 90%

<Ca sealing performance measurement>

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 edge. The films produced in Examples and Comparative Examples are attached to an aluminum foil / PET composite film "AL1N30 with PET" (aluminum foil: 30 μm, PET: 25 μm: product name manufactured by Tokai Toyo Aluminum Sales Co., Ltd.) and heated in a glove box. Using a laminator (Lamipacker DAiSY A4 (LPD2325) manufactured by Fujipla Co., Ltd.), it was bonded to non-alkali glass vapor-deposited with calcium to obtain a sample for evaluation.

When calcium comes into contact with water and becomes calcium oxide, it becomes transparent. Therefore, the intrusion of water into the evaluation sample can be evaluated by measuring the sealing distance X (mm) from the end of the evaluation sample to the calcium film.

First, the sealing distance from the end of the evaluation sample to the calcium film was measured by a Measuring Microscope MF-U manufactured by Mitutoyo, and this value was defined as X2.

Next, the evaluation sample was put into a constant temperature and humidity chamber set at a temperature of 85 ° C. and a relative humidity of 85% RH. The sealing distance X1 (mm) from the end of the evaluation sample to the calcium film after being put into the constant temperature and humidity chamber is the seal from the end of the evaluation sample to the calcium film before being put into the constant temperature and humidity chamber. The evaluation sample was taken out from the constant temperature and humidity chamber at a time increased by 0.1 mm from the stop distance X2 (mm), and the time was defined as the decrease start time t (hour).

The following Fick diffusion formula:
X1 = K√t
(In the formula, X1 is the sealing distance (mm) from the end of the evaluation sample to the calcium film after being put into the constant temperature and humidity chamber, and t is the reduction start time (X1 = X2 + 0.1). Time), and X2 is the sealing distance (mm) from the end of the evaluation sample to the calcium film before being put into the constant temperature and humidity chamber.)
The constant K was calculated based on the above.

Using the obtained K, the time when X became 2 mm was calculated as the time for starting water invasion into the calcium film. The higher the water blocking property, the slower the rate of water invasion, and the longer the water invasion start time.
Good (○): 120 hours or more Bad (×): 120 hours or less

<Measurement of water content>
The resin sheets produced in Examples and Comparative Examples were cut to a length of 70 mm and a width of 40 mm, folded into a well-dried quartz container, and directly connected to a Karl Fischer measuring instrument (CA100 type, manufactured by Mitsubishi Chemical Corporation). VA-21 type, manufactured by Mitsubishi Chemical Corporation). N ₂ gas stream, the temperature of the electric furnace was raised to 250 ° C., the desorbed water from the sample collected in the Karl Fischer test solution was measured the absolute amount of water in a conventional method. The ratio of the absolute amount of water to the mass of the measurement sample was calculated as the water content (ppm).

Table 1 below shows the composition and test results of the resin compositions of Examples and Comparative Examples.
From Table 1, it can be seen that the resin composition of the present invention can exhibit higher moisture shielding properties.

The resin composition of the present invention can exhibit higher moisture shielding properties, and is suitable for a sealing portion of a light emitting element such as an organic EL element, an optical semiconductor such as a high-brightness LED, and a light receiving element such as a solar cell.

Claims (13)

The following components (A) to (C):
(A) Thermoplastic resin;
A resin composition containing (B) a hygroscopic filler; and (C) a plate-like filler and having a water content of 1500 ppm or less. (A) The resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin resin. (B) The resin composition according to claim 1 or 2, wherein the content of the hygroscopic filler is 10% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition. The resin composition according to any one of claims 1 to 3, wherein the content of the plate-shaped filler is 10% by mass or more and 80% by mass or less with respect to 100% by mass of the non-volatile content of the resin composition. .. The method according to any one of claims 1 to 4, wherein the mass ratio of the (B) hygroscopic filler to the (C) plate-shaped filler (hygroscopic filler: plate-shaped filler) is 10: 1 to 1: 5. Resin composition. (B) The resin composition according to any one of claims 1 to 5, wherein the hygroscopic filler is semi-baked hydrotalcite. The resin composition according to any one of claims 1 to 6, wherein the plate-shaped filler is at least one selected from plate-shaped glass, unfired hydrotalcite, smectite, and synthetic phlogopite. (C) The resin composition according to any one of claims 1 to 7, wherein the plate-shaped filler has an average aspect ratio of 2 or more. A resin sheet having a support and a resin composition layer containing the resin composition according to any one of claims 1 to 8 provided on the support. The resin sheet according to claim 9, which is used for sealing an electronic device. The resin sheet according to claim 9, which is used for sealing an organic EL device. An electronic device sealed with the resin sheet according to claim 9. An organic EL device sealed with the resin sheet according to claim 9.