JP7318462B2 - Sealing resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealing resin composition, and more particularly to a sealing resin composition suitable for sealing electronic devices such as organic EL (Electroluminescence) devices and solar cells.

A method of sealing an electronic device, especially an electronic device vulnerable to moisture such as an organic EL (Electroluminescence) device and a solar cell, using a resin composition containing a hygroscopic filler in order to protect the electronic device from outside air containing moisture and the like. is known (Patent Document 1).

International publication 2017/057708 pamphlet

From the viewpoint of obtaining a sealing resin composition having high resistance to moisture permeation, it is desirable to increase the content of the hygroscopic filler in the resin composition. However, there arises a problem that the adhesiveness and transparency of the film are deteriorated. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a sealing resin composition which is excellent in moisture permeation resistance, adhesiveness and transparency.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a polyolefin resin contains a tackifier and a specific metal complex even when the hygroscopic filler is blended at a high content. In this case, the inventors have found that a resin composition having excellent adhesion and transparency in addition to moisture permeation resistance can be obtained, and have completed the present invention.

That is, the present invention has the following features.
[1] (A) polyolefin resin;
(B) a hygroscopic filler;
(C) a metal complex; and (D) a sealing resin composition containing a tackifier, wherein the content of (B) a hygroscopic filler with respect to 100% by mass of non-volatile components in the sealing resin composition is 45 % by mass, and (C) the metal complex is a metal complex in which a bidentate ligand whose two coordinating atoms are both oxygen atoms and a monodentate ligand whose coordinating atoms are oxygen atoms are bound to the central metal A sealing resin composition.
[2] The resin composition for sealing according to [1], wherein (B) the hygroscopic filler is semi-calcined hydrotalcite.
[3] The encapsulating resin composition according to [1] or [2], wherein the central metal of (C) the metal complex is aluminum or titanium.
[4] (C) The metal complex has the general formula (1):

(In the formula,
M represents a metal from period 2 to period 6 of the periodic table,
R ₁ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or represents an optionally substituted aralkyl group,
R ₂ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, or a substituted represents an aryl group that may be substituted, or an aralkyl group that may have a substituent,
X represents a monodentate ligand whose coordinating atom is an oxygen atom;
The solid line between the oxygen atom (O) and M in [ ] represents a covalent bond,
The dashed line between the oxygen atom (O) and M in [ ] represents a coordinate bond, and m is an integer of 3 or 4, n is an integer of 1 to 3, and m>n . )
The encapsulating resin composition according to any one of [1] to [4], which is a metal complex represented by
[5] The encapsulating resin composition according to [4], wherein M in formula (1) is aluminum or titanium.
[6] (A) The polyolefin resin according to any one of [1] to [5], including a polyolefin resin having an acid anhydride group and/or a polyolefin resin having an epoxy group. Resin composition for encapsulation.
[7] (A) The sealing resin according to any one of [1] to [5], wherein the polyolefin resin includes a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. Composition.
[8] (A) The encapsulant according to any one of [1] to [5], wherein the polyolefin resin contains a reaction product of a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. A resin composition for stopping.
[9] The encapsulation according to any one of [1] to [8], wherein the content of (C) the metal complex is 0.1 to 5% by mass with respect to 100% by mass of non-volatile components in the resin composition. resin composition for
[10] The sealing material according to any one of [1] to [9], wherein the content of (D) the tackifier is 5 to 40% by mass with respect to 100% by mass of non-volatile components in the resin composition. Resin composition.
[11] The encapsulating resin composition according to any one of [1] to [10], which is used for encapsulating electronic devices.
[12] The encapsulating resin composition of [11], wherein the electronic device is an organic EL device or a solar cell.
[13] A sealing sheet comprising a support and a layer of the resin composition according to any one of [1] to [12] formed on the support.
[14] An electronic device encapsulated with the encapsulating resin composition according to any one of [1] to [10].
[15] The electronic device of [14], wherein the electronic device is an organic EL device or a solar cell.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition for sealing which is excellent also in adhesiveness and transparency in addition to moisture-permeation resistance can be implement|achieved.

[Resin composition for encapsulation]
The encapsulating resin composition of the present invention (hereinafter also simply referred to as "resin composition") comprises, as essential components, (A) a polyolefin resin, (B) a hygroscopic filler, (C) a metal complex, and (D) Contains a tackifier.

<(A) Polyolefin resin>
The encapsulating resin composition of the present invention contains a polyolefin resin (hereinafter also referred to as "component (A)"). Any polyolefin-based resin can be used without any particular limitation as long as it has an olefin-derived skeleton. The olefin is preferably a monoolefin having one olefinic carbon-carbon double bond and/or a diolefin having two olefinic carbon-carbon double bonds. Preferred monoolefins include α-olefins such as ethylene, propylene, 1-butene, isobutylene (isobutene), 1-pentene, 1-hexene, 1-heptene and 1-octene. Preferred are 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like. Monoolefins and diolefins may be of one type or two or more types. Such polyolefin-based resins may be used alone or in combination of two or more.

Polyolefin resins may be homopolymers, random copolymers, or block copolymers. Further, the copolymer is (i) a copolymer of two or more monoolefins, (ii) a copolymer of a monoolefin and a diolefin, or (iii) a monoolefin and an unsaturated carboxylic acid ester (e.g., methyl methacrylate, etc.) and copolymers with ethylenically unsaturated compounds other than olefins (excluding diene-based monomers) such as aromatic vinyls (eg, styrene, etc.).

The polyolefin-based resin is preferably a polybutene-based resin or a polypropylene-based resin. Here, "polybutene resin" refers to a resin in which the main unit (maximum content unit) of all olefin monomer units constituting the polymer is derived from butene, and "polypropylene resin" constitutes the polymer. It refers to a resin in which the main unit (maximum content unit) of all the olefin monomer units is derived from propylene.

When the polybutene-based resin is a copolymer, examples of monomers other than butene include styrene, ethylene, propylene, and isoprene. When the polypropylene-based resin is a copolymer, examples of monomers other than propylene include ethylene, butene, and isoprene.

The polyolefin resin is a polyolefin resin having an acid anhydride group (that is, a carbonyloxycarbonyl group (-CO-O-CO-)) from the viewpoint of further improving the moisture permeability resistance of the encapsulating resin composition, and/or it may contain a polyolefin resin having an epoxy group. The acid anhydride group includes, for example, a group derived from succinic anhydride, a group derived from maleic anhydride, a group derived from glutaric anhydride, and the like. One or more acid anhydride groups can be used. A polyolefin resin having an acid anhydride group can be obtained, for example, by graft-modifying a polyolefin resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. Also, an unsaturated compound having an acid anhydride group may be radically copolymerized with an olefin. Similarly, the polyolefin resin having an epoxy group is, for example, an unsaturated compound having an epoxy group such as glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc., and the polyolefin resin is reacted under radical reaction conditions. It is obtained by graft modification at. Also, an unsaturated compound having an epoxy group may be radically copolymerized with an olefin.

As the polyolefin-based resin having an acid anhydride group, a polybutene-based resin having an acid anhydride group and a polypropylene-based resin having an acid anhydride group are preferable. Polybutene-based resins having epoxy groups and polypropylene-based resins having epoxy groups are preferable as polyolefin-based resins having epoxy groups.

In the polyolefin resin having acid anhydride groups, the concentration of acid anhydride groups in the resin is preferably 0.05 to 10 mmol/g, more preferably 0.1 to 5 mmol/g. The concentration of acid anhydride groups is obtained from the value of acid value defined as mg of potassium hydroxide required to neutralize the acid present in 1 g of resin according to JIS K 2501.

In polyolefin resins having epoxy groups, the concentration of epoxy groups in the resin 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.

In order to further improve the moisture permeation resistance of the encapsulating resin composition, the component (A) is in a mode in which the polyolefin resin contains a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. Preferably.

Such a component (A) can form a crosslinked structure by reacting the acid anhydride group and the epoxy group by heating. Thus, when the component (A) contains a reaction product of a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, the resin composition of the present invention provides sealing with further improved resistance to moisture permeation. It can form layers. The formation of the crosslinked structure can be performed after sealing with the resin composition (that is, after forming the sealing layer). In this case, it is desirable to form a crosslinked structure in the resin composition layer formed on the substrate, for example, at the time of production of the sealing sheet.

In the case where the component (A) contains a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, the reaction between the polyolefin resin having an epoxy group and the polyolefin resin having an acid anhydride group The amount ratio is not particularly limited as long as an appropriate crosslinked structure can be formed, but the molar ratio between the epoxy group and the acid anhydride group (epoxy group: acid anhydride group) is preferably 100:10 to 100:400, more preferably is 100:25 to 100:350, particularly preferably 100:40 to 100:300.

The number average molecular weight of the component (A) is not particularly limited, but it is possible to achieve good varnish coating properties when processing the sealing resin composition into a film and good compatibility with other components in the resin composition. From the viewpoint of providing solubility, it is preferably 1,000,000 or less, more preferably 750,000 or less, even more preferably 500,000 or less, and even more preferably 400,000 or less. On the other hand, it is preferably 2,000 or more from the viewpoint of preventing repelling during coating of the varnish of the sealing resin composition and improving the moisture permeation resistance and mechanical strength of the formed sealing resin composition layer. , is more preferably 10,000 or more, even more preferably 30,000 or more, and particularly preferably 50,000 or more. In addition, a number average molecular weight is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). The number-average molecular weight by the GPC method was measured using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. as a column, and toluene or the like as a mobile phase. can be measured at a column temperature of 40° C. using a standard polystyrene calibration curve.

Specific examples of the component (A) are described below.
As a specific example of the polypropylene-based resin, for example, "T-YP341" manufactured by Seiko PMC (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100 mass% total of propylene units and butene units: 29 mass %, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000), "T-YP279" manufactured by Seiko PMC (maleic anhydride-modified propylene-butene random copolymer, sum of propylene units and butene units Amount of butene units per 100% by mass: 36% by mass, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 35,000), "T-YP276" manufactured by Seiko PMC (glycidyl methacrylate-modified propylene- Butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units combined: 36% by mass, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 57,000), manufactured by Seiko PMC Co., Ltd. "T-YP312" (maleic anhydride-modified propylene-butene random copolymer, amount of butene units per 100% by mass of total propylene units and butene units: 29% by mass, acid anhydride group concentration: 0.464 mmol/ g, number average molecular weight: 60,900), "T-YP313" manufactured by Seiko PMC (glycidyl methacrylate-modified propylene-butene random copolymer, amount of butene units per 100% by mass of propylene units and butene units total: 29 mass %, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000) and the like.

Specific examples of polybutene-based resins include, for example, HV-1900 (manufactured by JX Energy): 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), BASF "Opanol B100" (polyisobutylene, viscosity average molecular weight: 1,110,000), BASF "N50SF" ( polyisobutylene, viscosity average molecular weight: 400,000) and the like.

The content of component (A) in the encapsulating resin composition of the present invention is not particularly limited. From the viewpoint of coatability and handleability (tack suppression) at times, the content is preferably 50% by mass or less, more preferably 45% by mass or less, with respect to 100% by mass of the non-volatile components in the resin composition. % by mass or less is more preferable. The content is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on 100% by mass of non-volatile components in the resin composition.

In addition, in the case where the component (A) contains a polyolefin resin having an acid anhydride group and/or a polyolefin resin having an epoxy group, the polyolefin resin having an acid anhydride group per component (A) as a whole and / Or the amount of polyolefin resin having an epoxy group is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, further preferably 15 to 70% by mass.

<(B) Hygroscopic filler>
The encapsulating resin composition of the present invention contains a hygroscopic filler (hereinafter also referred to as "component (B)").

The hygroscopic filler (B) is not particularly limited as long as it is a filler capable of absorbing moisture, but metal oxides and metal hydroxides are preferred. Specifically, metal oxides such as calcium oxide, magnesium oxide, strontium oxide, aluminum oxide, barium oxide, calcined hydrotalcite, calcined dolomite, calcium hydroxide, magnesium hydroxide, strontium hydroxide, aluminum hydroxide, water metal hydroxides such as barium oxide and semi-calcined hydrotalcite; Among them, semi-calcined hydrotalcite and calcined hydrotalcite are preferable from the viewpoint of hygroscopicity, and semi-calcined hydrotalcite is preferable from the viewpoint of transparency.

Calcined hydrotalcite and semi-calcined hydrotalcite, which are preferable as the hygroscopic filler, are described below. Hydrotalcite can be classified into unbaked hydrotalcite, semi-baked hydrotalcite, and calcined hydrotalcite, and semi-baked hydrotalcite is particularly preferable from the viewpoint of transparency and resistance to moisture permeation of the resin composition. . Uncalcined hydrotalcite is _{a metal} hydroxide having _a layered crystal structure typified by, for example, natural hydrotalcite ( _Mg6Al2 (OH) _16CO3.4H2O ). It consists of a layer [Mg _1−X Al _X (OH) ₂ ] ^X+ serving as a basic skeleton 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 hydrotalcite-like compounds 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)
(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ and Zn ²⁺ , M ³⁺ represents a trivalent metal ion such as Al ³⁺ and Fe ³⁺ , and A ⁿ⁻ represents CO ₃ ²⁻ , Cl ^- represents an n-valent anion such as NO ₃ ^- , where 0<x<1, 0≦m<1, and n is a positive number.)
In formula (I), M ²⁺ is preferably Mg ²⁺ , M ³⁺ is preferably Al ³⁺ and A ^n- is preferably CO ₃ ^2- .

M ²⁺ _x Al ₂ (OH) _2x+6−nz (A ⁿ⁻ ) _z ·mH ₂ O (II)
(In the formula, M ²⁺ represents a divalent metal ion such as Mg ²⁺ and Zn ²⁺ , A ^n- represents an n-valent anion such as CO ₃ ²⁻ , Cl ⁻ , NO ₃ ⁻ , and 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.)
In formula (II), M ²⁺ is preferably Mg ²⁺ and 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 inter-layer water is reduced or eliminated, which is obtained by calcining uncalcined hydrotalcite. The term "interlayer water" refers to "H ₂ O" described in the compositional formulas of the above-described uncalcined natural hydrotalcite and hydrotalcite-like compound, when explained using the compositional formulas.

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

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

The above "saturated water absorption rate" is obtained by weighing 1.5 g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite with a balance, measuring the initial mass, and measuring the initial mass at 60 ° C. and 90% under atmospheric pressure. Refers to the mass increase rate relative to the initial mass when left standing for 200 hours in a small environmental tester (SH-222 manufactured by Espec Co., Ltd.) set to % RH (relative humidity), and the following formula (i):
Saturated water absorption (mass%) = 100 × (mass after moisture absorption - initial mass) / initial mass (i)
can be found at

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

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

Thermogravimetric analysis was carried out using TG/DTA EXSTAR6300 manufactured by Hitachi High-Tech Science Co., Ltd., weighing 5 mg of hydrotalcite in an aluminum sample pan, opening the pan without a lid, under an atmosphere of nitrogen flow rate of 200 mL/min. It can be carried out from 30° C. to 550° C. under the condition of a temperature increase rate of 10° C./min. The thermal weight loss rate is expressed by the following formula (ii):
Thermal weight loss rate (mass%)
= 100 x (mass before heating - mass when reaching predetermined temperature) / mass before heating (ii)
can be found at

Also, uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction. Semi-calcined hydrotalcite shows a peak split into two near 2θ of 8 to 18° by powder X-ray diffraction, or a peak having a shoulder due to the synthesis of two peaks, and the peak or shoulder appears on the low angle side. The relative intensity ratio (low-angle diffraction intensity/high-angle diffraction intensity) of the diffraction intensity (=low-angle diffraction intensity) and the peak or shoulder diffraction intensity (=high-angle diffraction intensity) appearing on the high-angle side is 0.001. ~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 and the peak or shoulder appearing on the high angle side is within the above range. outside. Calcined hydrotalcite has no characteristic peak in the region of 8° to 18° and a characteristic peak at 43°. Powder X-ray diffraction measurement was performed using a powder X-ray diffractometer (manufactured by PANalytical, Empyrean), anticathode CuKα (1.5405 Å), voltage: 45 V, current: 40 mA, sampling width: 0.0260°, scanning speed: 0 0657°/s, measurement diffraction angle range (2θ): 5.0131 to 79.9711°. The peak search is performed using the peak search function of the software attached to the diffractometer. .00°, method: minimum value of second derivative”.

Specific examples of uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite include the following.
・DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 15 m ² /g)
・ DHT-4A-2 (manufactured by Kyowa Chemical Industry Co., Ltd.): semi-calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 13 m ² /g)
・KW-2200 (manufactured by Kyowa Chemical Industry Co., Ltd.): calcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 146 m ² /g)
・DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.): uncalcined hydrotalcite (average particle size: 400 nm, BET specific surface area: 10 m ² /g)

The average particle diameter of the hygroscopic filler is not particularly limited, but is preferably 25 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less from the viewpoint of the effect on the sealing object and moisture permeation resistance. 5 μm or less is particularly preferred, and 1 μm or less is most preferred. On the other hand, from the viewpoint of the dispersibility of the hygroscopic filler and the viscosity of the resin composition, the average particle diameter is preferably 0.001 μm or more, more preferably 0.01 μm or more, and even more preferably 0.1 μm or more.

The average particle size of the hygroscopic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the hygroscopic filler can be prepared on a volume basis using a laser diffraction particle size distribution measuring apparatus, and the median diameter can be used as the average particle size for measurement. As a measurement sample, a hygroscopic filler dispersed in water by ultrasonic waves can be preferably used. LA-500 manufactured by Horiba Ltd. can be used as the laser diffraction particle size distribution analyzer.

Among the hygroscopic fillers, hydrotalcite preferably has an average particle size of 1 to 1,000 nm, more preferably 10 to 800 nm. The average particle size of 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 particle size distribution measurement (JIS Z 8825).

Among the hygroscopic fillers, hydrotalcite preferably has a BET specific surface area of 1 to 250 m ² /g, more preferably 5 to 200 m ² /g. The BET specific surface area of hydrotalcite can be calculated using the BET multipoint method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM Model 1210, manufactured by Mountec) according to the BET method. .

Component (B) can be used after being surface-treated with a surface-treating agent. Examples of surface treatment agents that can be used for surface treatment include higher fatty acids, alkylsilanes, silane coupling agents, and the like, with higher fatty acids and alkylsilanes being preferred. 1 type(s) or 2 or more types can be used for a surface treating agent.

Examples of higher fatty acids include higher fatty acids having 18 or more carbon atoms, such as stearic acid, montanic acid, myristic acid, and palmitic acid. Among them, stearic acid is preferred. These may be used singly or in combination of two or more. Examples of alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltrimethoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl ( 3-(trimethoxysilyl)propyl)ammonium chloride and the like. These may be used singly or in combination of two or more. Examples of silane coupling agents include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. epoxy-based silane coupling agents such as silane; mercapto-based 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 silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane and vinylmethyldiethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; 3-acryloxypropyltrimethoxy Acrylate-based silane coupling agents such as silane and 3-methacryloxypropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, bis(triethoxysilylpropyl) disulfide, bis(triethoxysilylpropyl) ) sulfide-based silane coupling agents such as tetrasulfide; These may be used singly or in combination of two or more.

The surface treatment of component (B) can be carried out, for example, by adding and spraying a surface treatment agent while stirring untreated component (B) in a mixer at room temperature and stirring for 5 to 60 minutes. As the mixer, known mixers can be used, and examples thereof include blenders such as V blenders, ribbon blenders and bubble cone blenders, mixers such as Henschel mixers and concrete mixers, ball mills and cutter mills. In addition, when the hygroscopic material is pulverized with a ball mill or the like, it is also possible to mix the higher fatty acid, the alkylsilanes or the silane coupling agent with the hygroscopic material for surface treatment. The treatment amount of the surface treatment agent varies depending on the type of component (B) or the type of surface treatment agent, but is preferably 1 to 10 parts by weight per 100 parts by weight of component (B).

The content of component (B) in the resin composition is more than 45% by mass with respect to 100% by mass of non-volatile components in the resin composition from the viewpoint of resistance to moisture permeation. The content is preferably 46% by mass or more, more preferably 48% by mass or more, and still more preferably 50% by mass or more. The upper limit of the content is not particularly limited as long as the effect of the present invention is exhibited, but from the viewpoint of adhesiveness and transparency of the resin composition, relative to 100% by mass of non-volatile components in the resin composition, preferably It is 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

<(C) Metal Complex>
The resin composition of the present invention contains a metal complex (hereinafter also referred to as "component (C)"). As the (C) metal complex in the present invention, a metal complex in which a bidentate ligand whose two coordinating atoms are both oxygen atoms and a monodentate ligand whose coordinating atoms are oxygen atoms are bonded to the central metal is used. do.

In the present invention, a metal complex is a chemical species in which other atoms, molecules, or ions are bonded to metal atoms or ions. Also, ligand refers to a molecule or ion that binds to a metal atom or ion. Atoms directly involved in the bond are called coordinating atoms, ligands with two coordinating atoms are called bidentate ligands, and ligands with one coordinating atom are called monodentate ligands.

Component (C) is a bidentate ligand whose two coordinating atoms are both oxygen atoms (hereinafter also abbreviated as “oxygen/bidentate ligand”) and a monodentate ligand whose coordinating atom is an oxygen atom. It is not particularly limited as long as it is a metal complex having a structure in which an element (hereinafter also abbreviated as "oxygen/monodentate ligand") is bound to a central metal, and known metal complexes satisfying this structure can be used. . Among them, metal complexes in which the central metal is a metal from the 2nd to 6th period of the periodic table are preferable, more preferably metal complexes in which the central metal is a metal from the 3rd to the 5th period of the periodic table, and still more preferably a central metal A metal complex in which the metal is Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, more preferably a metal complex in which the central metal is Al, Ti, or Zr be. From the viewpoint of the transparency of the resin composition, metal complexes in which the central metal is Al (aluminum) or Ti (titanium) are particularly preferred. (C) Component can use 1 type(s) or 2 or more types.

Examples of the oxygen/bidentate ligand include compounds represented by the following formula (a).

In formula (a), R ₁ , R ₂ and R ₃ have the same meanings as those in formula (1) below.

The compound represented by the formula (a) represents an oxygen/bidentate ligand before coordinating to the central metal. In the present invention, the oxygen/bidentate ligand in a state coordinated to the central metal and the oxygen/bidentate ligand before being coordinated to the central metal are referred to as "oxygen/bidentate ligands" without particular distinction. It is sometimes referred to as a "dentate ligand". Specific examples of the compound represented by the formula (a) are synonymous with specific examples of the oxygen/bidentate ligand in the metal complex represented by the formula (1) below.

Examples of oxygen/monodentate ligands include alkoxide anions (RO ⁻ ) and carboxylate anions (RCOO ⁻ ). Specific examples of the oxygen/monodentate ligand are also synonymous with specific examples of the oxygen/monodentate ligand in the metal complex represented by formula (1) below. In the present invention, the oxygen/monodentate ligand in a state coordinated to the central metal, and the oxygen/monodentate ligand before being coordinated to the central metal (alcohol (ROH), carboxylic acid (RCOOH)) are particularly It may be referred to as "oxygen/monodentate ligand" without distinction.

In the metal complex of component (C), the number of oxygen-bidentate ligands is 1 or more, preferably 1 or more and 3 or less, more preferably 2. When the number of oxygen-bidentate ligands is plural, they may be the same ligand or different ligands, but the same ligand is preferred. The number of oxygen/monodentate ligands is 1 or more, preferably 1 or more and 3 or less, more preferably 2 or 3. When there are a plurality of oxygen/monodentate ligands, they may be the same ligand or different ligands, but the same ligand is preferred.

Component (C) is more preferably a metal complex represented by the following general formula (1) (hereinafter also referred to as a metal complex of formula (1)).

In formula (1),
M is the central metal of the metal complex and represents a metal from the 2nd to the 6th periods of the periodic table. It is preferably a 3rd to 5th period metal, more preferably Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ge, Zr, In, or Sn, still more preferably Al, Ti , or Zr, and particularly preferably Al (aluminum) or Ti (titanium).
R ₁ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group.
_R2 represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, or an aralkyl group.
X represents an oxygen/monodentate ligand.

A solid line between the oxygen atom (O) and M in [ ] represents a covalent bond, and a dashed line between the oxygen atom (O) and M in [ ] represents a coordinate bond.

m is an integer of 3 or 4, n is an integer of 1 to 3, and m>n.

Alkyl groups in R ₁ , R ₂ and R ₃ may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Alkyl groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1-ethylpropyl group, Examples include hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group and 2-ethylbutyl group. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an optionally substituted amino group, and the like.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Examples of the amino group optionally having a substituent include amino group, mono- or di-alkylamino group (e.g., methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group , dibutylamino group), mono- or di-cycloalkylamino group (e.g., cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino group (e.g., phenylamino group), mono- or di-aralkyl Examples include amino groups (eg, benzylamino group, dibenzylamino group), heterocyclic amino groups (eg, pyridylamino group), and the like.

The alkoxy group for R ₁ , R ₂ and R ₃ is preferably an alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec -butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group and the like. An alkoxy group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an optionally substituted amino group, and the like. Specific examples of the halogen atom and specific examples of the amino group optionally having a substituent are the same as those described above.

The number of carbon atoms in the aryl group in R ₁ , R ₂ and R ₃ is preferably 6-18, more preferably 6-14. Examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl and 9-anthryl groups. The aryl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, An amino group optionally having a substituent and the like can be mentioned.

The above alkenyl groups may be straight or branched. The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms. For example, ethenyl group (that is, vinyl group), 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2 -butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 4-methyl-3-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group and the like. be done. Examples of the substituent which the alkenyl group may have include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like. Specific examples of the halogen atom and specific examples of the amino group optionally having a substituent are the same as those described above.

The above alkynyl groups may be straight or branched. The number of carbon atoms in the alkynyl group is preferably 2-10, more preferably 2-6. For example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 4-methyl-2-pentynyl group and the like. Examples of the substituent which the alkynyl group may have include a halogen atom, a hydroxy group, an amino group which may have a substituent, and the like. Specific examples of the halogen atom and specific examples of the amino group optionally having a substituent are the same as those described above.

The aralkyl group in R ₁ , R ₂ and R ₃ preferably has 7 to 16 carbon atoms. Examples thereof include benzyl group, phenethyl group, naphthylmethyl group, phenylpropyl group and the like. The aralkyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an optionally substituted amino group, and the like. Specific examples of the halogen atom and specific examples of the amino group optionally having a substituent are the same as those described above.

The alkoxycarbonyl group for R ₂ is preferably an alkoxycarbonyl group having 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxy carbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group and the like. An alkoxycarbonyl group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an optionally substituted amino group, and the like. Specific examples of the halogen atom are the same as those of the halogen atom which is the substituent of the alkyl group described above, and specific examples of the amino group which may have a substituent are the substituents which are the substituent of the alkyl group described above. It is the same as that of an optionally substituted amino group.

In the formula, the oxygen/monodentate ligand represented by X is usually a conjugate base of Bronsted acid, such as alkoxide anion (RO ⁻ ) and carboxylate anion (RCOO ⁻ ).

In alkoxide anions (RO ⁻ ), the organic group R can be either an aliphatic group or an aromatic group. Also, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Alkoxide anions (RO ⁻ ) include, for example, methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, sec-butoxide, tert-butoxide, pentyl oxide, hexyl oxide and the like.

In the carboxylate anion (RCOO ⁻ ), the organic group R can be either an aliphatic group or an aromatic group. Also, the aliphatic group may be either a saturated aliphatic group or an unsaturated aliphatic group. The number of carbon atoms in the organic group R is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Examples of carboxylate anions (RCOO ⁻ ) include carboxylate anions corresponding to carboxylic acids such as acetic acid, propionic acid and benzoic acid.

[ ] in the formula represents an oxygen/bidentate ligand. Specific examples of oxygen/bidentate ligands include acetylacetone, 3-methyl-2,4-pentanedione, acetylacetaldehyde, 2,4-hexanedione, 2,4-heptanedione, 5-methyl-2,4 -hexanedione, 5,5-dimethyl-2,4-hexanedione, benzoylacetone, benzoylacetophenone, salicylaldehyde, 1,1,1-trifluoroacetylacetone, 1,1,1,5,5,5-hexafluoro Acetylacetone, 3-methoxy-2,4-pentanedione, 3-cyano-2,4-pentanedione, 3-nitro-2,4-pentanedione, 3-chloro-2,4-pentanedione, acetoacetic acid, aceto Methyl acetate, ethyl acetoacetate, propyl acetoacetate, salicylic acid, methyl salicylate, malonic acid, dimethyl malonate, diethyl malonate and the like. When coordinated to the central metal, the oxygen-bidentate ligand has one or more protons removed from it.

Specific examples of the metal complex of formula (1) include the following. Examples of metal complexes in which the central metal M is Al (aluminum) include aluminum alkylacetoacetate diisopropylate (aluminum 9-octadecynylacetoacetate diisopropoxide), aluminum ethylacetoacetate diisopropylate, and aluminum ethylacetoacetate. di-n-butylate, aluminum propylacetoacetate diisopropylate, aluminum n-butylacetoacetate diisopropylate and the like.

Examples of metal complexes in which the central metal M is Ti (titanium) include titanium allylacetoacetate triisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis ( tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), titanium methylphenoxide, titanium oxide bis(pentanedionate) and the like.

In addition, metal complexes in which the central metal M is Zr (zirconium) include, for example, zirconium allylacetoacetate triisopropoxide, zirconium di-n-butoxide (bis-2,4-pentanedionate), zirconium diisopropoxide ( bis-2,4-pentanedionate), zirconium diisopropoxide bis(tetramethylheptanedionate), zirconium diisopropoxide bis(ethylacetoacetate), zirconium butoxide (acetylacetate) (bisethylacetoacetate), and zirconium tributoxy monoacetylacetonate.

The content of component (C) in the resin composition is not particularly limited, but from the viewpoint of adhesiveness and transparency of the resin composition, it is 0.1% by mass with respect to 100% by mass of non-volatile components in the resin composition. The above is preferable, and 0.3% by mass or more is more preferable. In addition, from the viewpoint of easily suppressing the influence of outgassing derived from the component (C) on the sealing object, the content is preferably 5% by mass or less, and 3% by mass with respect to 100% by mass of the nonvolatile components in the resin composition. % or less is more preferable.

In one embodiment of the present invention, the content of component (C) in the resin composition of the present invention is preferably 0.1 to 5% by mass with respect to 100% by mass of non-volatile components in the resin composition. Yes, more preferably 0.3 to 3% by mass.

A metal complex different from the component (C) of the present invention, for example, a metal complex in which an oxygen/bidentate ligand is bound to a central metal, but an oxygen/monodentate ligand is not bound to the central metal. Even if it is a metal complex, a metal complex in which an oxygen/monodentate ligand is bound to the central metal, or a metal complex in which an oxygen/bidentate ligand is not bound to the central metal, the desired performance is excellent. However, it is not possible to realize a resin composition that has both adhesiveness, transparency and resistance to moisture permeation. Although the reason for this is not necessarily clear, the metal complex having a structure in which the oxygen/bidentate ligand and the oxygen/monodentate ligand, which are the component (C) of the present invention, are bonded to the central metal, is susceptible to hydrolysis.・Since it has a monodentate ligand, it is easy to modify the surface of the hygroscopic filler, which is the component (B), and the component (B) can be sufficiently dispersed in the resin composition. When it is attached to an object to be sealed, the oxygen/bidentate ligand exchanges chelates with the functional groups on the surface of the object to be sealed, such as glass, plastic, inorganic film, etc., to form a strong bond (B). It is presumed that even when the components are blended at a high content, the resin composition will be excellent in adhesiveness and transparency in addition to moisture permeation resistance.

<(D) Tackifier>
The encapsulating resin composition of the present invention contains a tackifier (hereinafter also abbreviated as "component (D)").

The tackifier is not particularly limited, and includes terpene-based resins, terpene-phenolic resins, rosin-based resins, hydrogenated terpene-based resins, aromatic modified terpene-based resins, coumarone resins, indene resins, petroleum resins (aliphatic petroleum resins, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene (hereinafter also abbreviated as "DCPD") petroleum resins, Hydrogenated dicyclopentadiene petroleum resins, etc.), etc., but from the viewpoint of adhesiveness and transparency, dicyclopentadiene petroleum resins and hydrogenated dicyclopentadiene petroleum resins are more preferred, and hydrogenated dicyclopentadiene petroleum resins are more preferred. Petroleum resins are particularly preferred.

The content of the component (D) in the resin composition is not particularly limited, but from the viewpoint of the adhesiveness of the resin composition, etc., it is preferably 5% by mass or more with respect to 100% by mass of the non-volatile components in the resin composition. 10% by mass or more is more preferable, and 15% by mass or more is even more preferable. Further, from the viewpoint of adhesion stability in a high temperature range, the content is preferably 40% by mass or less, more preferably 30% by mass or less, and 25% by mass or less with respect to 100% by mass of non-volatile components in the resin composition. More preferred.

In one embodiment of the present invention, the content of component (D) in the resin composition of the present invention is preferably 5 to 40% by mass with respect to 100% by mass of non-volatile components in the resin composition, More preferably 10 to 30% by mass, still more preferably 15 to 25% by mass.

<(E) Additive>
The resin composition of the present invention contains softening agents such as mineral oil softeners, vegetable oil softeners, subfactices, fatty acids, fatty acid salts, synthetic organic compounds, synthetic oils, etc.; Agent; Organic filler such as rubber particles, silicone powder, nylon powder, fluororesin powder; Antifoaming agent or leveling agent such as silicone, fluorine, or polymer; Triazole compound, thiazole compound, triazine compound, porphyrin compound, etc. thickening agents such as orben and bentone; antioxidants; heat stabilizers; and additives such as light stabilizers. Inorganic fillers other than hygroscopic fillers may also be blended. Examples of such inorganic fillers include silica, mica, alumina, barium sulfate, talc, clay, mica powder, calcium carbonate, magnesium carbonate, boron nitride, aluminum borate, barium titanate, strontium titanate, and calcium titanate. , magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like.

<(F) Curing Agent and/or Curing Accelerator>
The resin composition of the present invention may contain a curing agent and/or a curing accelerator, for example, when it contains a polyisobutylene resin having an epoxy group. The curing agent and/or curing accelerator may be used alone or in combination of two or more. Examples of curing agents include imidazole compounds, tertiary/quaternary amine compounds, dimethylurea compounds, organic phosphine compounds, primary/secondary amine compounds, and the like. Examples of curing accelerators include imidazole compounds, tertiary/quaternary amine compounds, dimethylurea compounds, and organic phosphine compounds.

Examples of imidazole compounds as curing agents and/or curing accelerators in the present invention include 1H-imidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl -2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6-(2 '-Undecylimidazolyl-(1'))-ethyl-s-triazine, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole , 2-phenylimidazole, 2-dodecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2′- methylimidazolyl-(1′)-ethyl-s-triazine, 2,4-diamino-6-(2′-methylimidazolyl-(1′))-ethyl-s-triazine isocyanuric acid adduct, etc. imidazole Specific examples of the compounds include Curazole 2MZ, 2P4MZ, 2E4MZ, 2E4MZ-CN, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2PHZ, 1B2MZ, 1B2PZ, 2PZ, C17Z, 1.2DMZ, 2P4MHZ-PW, 2MZ-A, 2MA-OK (both manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.

The tertiary/quaternary amine-based curing agent as the curing agent and/or curing accelerator in the present invention is not particularly limited, but quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU (1 ,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenol salt, DBU-octylate, DBU-p- diazabicyclo compounds such as toluenesulfonate, DBU-formate, DBU-phenol novolak resin salt; benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol (TAP), etc. tertiary amines and salts thereof, aromatic dimethylurea, aliphatic dimethylurea and other dimethylurea compounds;

Examples of the primary/secondary amine compound as the curing agent in the present invention include aliphatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, 1 , 3-bisaminomethylcyclohexane, dipropylenediamine, diethylaminopropylamine, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane and the like, N-aminoethylpiverazine which is an alicyclic amine, 1,4-bis(3-aminopropyl)piperazine, aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diethyltoluenediamine. . Specific examples of the primary/secondary amine compounds include Kayahard AA (manufactured by Nippon Kayaku Co., Ltd.: 4,4'-diamino-3,3'-dimethyldiphenylmethane).

Specific examples of dimethylurea compounds as curing agents and/or curing accelerators in the present invention include DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) and U-CAT3512T (manufactured by San-Apro Co., Ltd.). and aromatic dimethyl urea such as U-CAT3503N (manufactured by San-Apro Co., Ltd.). Among them, aromatic dimethylurea is preferably used from the viewpoint of curability.

Examples of organic phosphine compounds as curing agents and/or curing accelerators in the present invention include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphoniumthiocyanate, tetraphenylphosphoniumthiocyanate, butyltriphenylphosphoniumthiocyanate, triphenylphosphinetriphenylborane and the like. Specific examples of organic phosphine compounds include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (manufactured by Hokko Chemical Industry Co., Ltd.).

The content of the curing agent and/or curing accelerator in the resin composition is not particularly limited, but from the viewpoint of preventing a decrease in the transparency of the sealing layer (resin composition layer), etc. 5 mass % or less is preferable with respect to 100 mass % of non-volatile components, and 1 mass % or less is more preferable. On the other hand, from the viewpoint of suppressing tackiness of the sealing layer, the content is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition. .

<(G) Organic solvent>
The resin composition of the present invention contains an organic solvent, for example, from the viewpoint of the coating properties of the resin composition when producing a sheet for encapsulation in which a layer of the resin composition is formed on a support, which will be described later. can be compounded. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (hereinafter also abbreviated as "MEK") and cyclohexanone, and acetic esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. , cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Such organic solvents may be used alone or in combination of two or more. Although the amount of the organic solvent is not particularly limited, it is preferable to use an amount such that the viscosity (25° C.) of the resin composition is 300 to 2000 mPa·s from the viewpoint of coatability.

<Method for producing resin composition>
The resin composition of the present invention can be produced by mixing the above components (including at least components (A) to (D)) using a kneading roller, a rotating mixer, or the like.

<Sheet for sealing>
For example, the resin composition of the present invention prepared as a varnish by blending an organic solvent is coated on a support, and the resulting coating film is dried by heating or blowing hot air to obtain a coating of the present invention on the support. A sheet for sealing, which is a sheet on which a layer of the resin composition is formed, is obtained. In the case of a sealing sheet prepared by using a resin composition containing a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group as the component (A) in the resin composition, during its preparation, By reacting the acid anhydride group and the epoxy group to form a crosslinked structure, the moisture permeation resistance of the resin composition layer is increased, and the sealing performance (blocking performance of moisture and oxygen in the air, etc.) is obtained.

Supports used for sealing sheets include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonates and polyimides. plastic film. PET is particularly preferable as the plastic film. Also, the support may be a metal foil such as an aluminum foil, a stainless steel foil, or a copper foil. The support may be subjected to matte treatment, corona treatment, or release treatment (hereinafter, "release-treated support" is also referred to as "releasable support"). Examples of the mold release treatment include mold release treatment using a mold release agent such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent. In the present invention, when the support has a release layer, the release layer is also considered part of the support. Although the thickness of the support is not particularly limited, it is preferably 20 to 200 μm, more preferably 20 to 125 μm from the viewpoint of handleability.

The peelable support is a support whose one side on which a layer of the resin composition of the present invention is formed has been subjected to release treatment, and the sheet for sealing is applied before actually using it to form a sealing structure. It is a support that is peeled off. For this reason, the peelable support does not necessarily need to be moisture-proof, but from the viewpoint of preventing moisture from entering the layer of the resin composition during the storage period until the encapsulating sheet is subjected to encapsulation. , preferably have moisture resistance. In order to improve the moisture resistance of the sealing sheet, a plastic film having a barrier layer may be used as a support (hereinafter, such a plastic film having a barrier layer is also referred to as "moisture-proof support"). Examples of the barrier layer include nitrides such as silicon nitride, oxides such as aluminum oxide, stainless steel foil, and metal foil such as aluminum foil. The plastic film includes the plastic films described above. A commercially available plastic film having a barrier layer may be used. Also, the moisture-proof support may be a composite laminated film of a metal foil and a plastic film. For example, commercial products of polyethylene terephthalate film with aluminum foil include "PET Tsuki AL1N30" manufactured by Tokai Toyo Aluminum Sales Co., Ltd., "PET Tsuki AL3025" manufactured by Fukuda Metal Co., Ltd., and the like. In addition, those having a multi-layer structure of two or more layers, for example, those obtained by laminating the above plastic film and the above metal foil via an adhesive can also be used. This product is inexpensive and advantageous from the viewpoint of handling.

In the sheet for sealing, the layer of the resin composition may be protected with a protective film. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched. It is preferable to use the same plastic film as the support as the protective film. The protective film may also be subjected to matte treatment, corona treatment, or release treatment. Although the thickness of the protective film is not particularly limited, it is usually 1 to 150 μm, preferably 10 to 100 μm.

If a support having moisture resistance and high transmittance is used as the support for the sealing sheet, the sealing sheet can be laminated to the object to be sealed to provide high resistance to moisture permeation. A sealed structure can be formed. Examples of such moisture-proof and high-transmittance supports include plastic films having inorganic substances such as silicon oxide (silica), silicon nitride, SiCN, and amorphous silicon vapor-deposited on their surfaces. Examples of plastic films include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonates, and polyimides. PET is particularly preferable as the plastic film. Examples of commercially available moisture-proof plastic films include Techbarrier HX, AX, LX, and L series (manufactured by Mitsubishi Plastics) and X-BARRIER (manufactured by Mitsubishi Plastics), which has a further improved moisture-proof effect. be done. As the support, one having a multi-layer structure of two or more layers may be used.

In the case of a sealing sheet having a peelable support, after laminating the sealing sheet to the sealing object, the support is peeled off and a separately prepared sealing base material (moisture-proof plastic film, metal foil such as copper foil and aluminum foil) can be laminated.

A circularly polarizing plate can be used as the support of the sealing sheet of the present invention. A circularly polarizing plate is generally composed of a polarizing plate and a quarter-wave plate. When a circularly polarizing plate is used as the support, a quarter-wave plate is generally arranged on the resin composition layer side. Further, when a support containing both a circularly polarizing plate and a moisture-proof support is used, the moisture-proof support is preferably arranged on the resin composition layer side, and the quarter-wave plate of the circularly polarizing plate is preferably arranged on the moisture-proof support side. placed in The moisture-proof support and the circularly polarizing plate can be adhered with an adhesive or the like, and the adhesive is not particularly limited as long as it is highly transparent, and examples thereof include acrylic adhesives and polyvinyl alcohol adhesives. etc. are used.

In addition, the circularly polarizing plate can be provided with a protective film that protects the polarizer (polarizing plate), and a known protective film can be used. Protective films described in pamphlet No. 2014/003189 and the like can be mentioned.

In the sealing sheet of the present invention, the support preferably comprises at least one selected from a peelable support, a moisture-proof support and a circularly polarizing plate.

<Electronic device>
When encapsulating an electronic device with the resin composition of the present invention, it is preferable to perform encapsulation using the encapsulating sheet. That is, by laminating the sheet for encapsulation of the present invention on the electronic device portion where the encapsulation structure is to be provided, an electronic device encapsulated with the resin composition for encapsulation of the present invention can be obtained.

Since the encapsulating resin composition of the present invention is excellent in moisture permeability resistance, adhesiveness and transparency, it is suitable for use in electronic devices, particularly organic EL devices and solar cells that require these characteristics. It can be suitably used as a sealing resin composition.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" in the amounts of components and copolymer units mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

Raw materials used in Examples and Comparative Examples are as follows.
(A) Polyolefin resin T-YP312 (manufactured by Seiko PMC): Maleic anhydride-modified propylene-butene copolymer (propylene unit/butene unit = 71%/29%, acid anhydride group concentration: 0.464 mmol/ g, number average molecular weight: 60,900) 40% toluene solution T-YP313 (manufactured by Seiko PMC): glycidyl methacrylate-modified propylene-butene copolymer (propylene unit / butene unit = 71% / 29%, epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000) 40% toluene solution T-YP341 (manufactured by Seiko PMC): Glycidyl methacrylate-modified propylene-butene random copolymer (propylene unit/butene unit: 71 %/29%, glycidyl group concentration: 0.638 mmol/g, number average molecular weight: 155,000) 20% silicone solution HV-1900 (manufactured by JX Energy): 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)

(B) Hygroscopic filler DHT-4C (manufactured by Kyowa Chemical Industry Co., Ltd.): semi-calcined hydrotalcite (abbreviated as “semi-calcined HT” in Table 1) (average particle size: 400 nm, BET specific surface area: 15 m ² /g)

(C) Metal complex Aluminum chelate M (manufactured by Kawaken Fine Chemicals Co., Ltd.): aluminum alkylacetoacetate diisopropylate KR38S (manufactured by Ajinomoto Fine-Techno Co., Ltd.): isopropyl tris (dioctylpyrophosphate) titanate Organics ZC540 (Matsumoto Fine Chemicals) company): zirconium tributoxy monoacetylacetonate ORGATIX ZC320 (manufactured by Matsumoto Fine Chemicals Co., Ltd.): zirconium stearate

(D) Tackifier Alcon P125 (manufactured by Arakawa Chemical Co., Ltd.): Cyclohexane ring-containing saturated hydrocarbon resin, softening point 125°C
・ T-REZ HA125 (manufactured by TonenGeneral Co., Ltd.): Hydrogenated DCPD type hydrocarbon resin (softening point 125 ° C.)

(F) Curing agent/anion-polymerizable amine-based curing agent (2,4,6-tris(diaminomethyl)phenol, hereinafter abbreviated as “TAP”)

(G) Organic solvent/toluene

Other ・Swasol #1000 (manufactured by Maruzen Oil Co., Ltd.): Aromatic mixed solvent

After preparing a varnish of the resin composition at the compounding ratio shown in Table 1 according to the following procedure, a sealing sheet was produced.
<Example 1>
77 parts of a cyclohexane ring-containing saturated hydrocarbon resin (Alcon P125, 60% Swarsol solution), 35 parts of maleic anhydride-modified liquid polyisobutylene (HV-300M), 60 parts of polybutene (HV-1900), aluminum alkylacetoacetate diisopropyl A mixture was obtained by dispersing 1.5 parts of latoate (aluminum chelate M) and 270 parts of semi-calcined hydrotalcite (DHT-4C) with a triple roll. 40 parts of a glycidyl methacrylate-modified polypropylene-polybutene copolymer (T-YP341, 20% silicone solution), 0.5 parts of an anionic polymerizable amine curing agent (TAP) and 170 parts of toluene were added to the resulting mixture, The resulting mixture was uniformly dispersed in a high-speed rotating mixer to obtain a resin composition varnish. A varnish was evenly applied to the release-treated surface of a polyethylene terephthalate film (thickness: 38 μm) (hereinafter referred to as PET film) treated with a silicone-based release agent using a die coater, and heated at 140° C. for 30 minutes. A resin composition layer having a thickness of 20 μm (amount of residual solvent in the resin composition layer: about 1% by mass) is formed, and then a cover film (a PET film (thickness of 38 μm) treated with a silicone release agent) is formed. were pasted together to obtain a sealing sheet.

<Example 2>
Sealing was carried out in the same manner as in Example 1, except that 1.5 parts of zirconium tributoxy monoacetylacetonate (Orgatics ZC540) was used instead of 1.5 parts of aluminum alkyl acetoacetate diisopropylate (aluminum chelate M). A sealing sheet was obtained.

<Example 3>
Using 77 parts of hydrogenated DCPD type hydrocarbon resin (T-REZ HA125) instead of 77 parts of cyclohexane ring-containing saturated hydrocarbon resin (Alcon P125, 60% silicone solution), aluminum alkylacetoacetate diisopropylate (aluminum chelate M ) was changed to 1 part, and the added amount of semi-calcined hydrotalcite (DHT-4C) was changed to 200 parts.

<Example 4>
In the same manner as in Example 1, except that polybutene (HV-1900) was not added and the amount of cyclohexane ring-containing saturated hydrocarbon resin (Alcon P125, 60% silicone solution) was 137 parts. got a sheet.

<Example 5>
The procedure of Example 1 was repeated except that the amount of aluminum alkylacetoacetate diisopropylate (aluminum chelate M) was 1.8 parts and the amount of semi-calcined hydrotalcite (DHT-4C) was 350 parts. to obtain a sealing sheet.

<Example 6>
77 parts of cyclohexane ring-containing saturated hydrocarbon resin (Alcon P125, 60% silicone solution), 95 parts of polybutene (HV-1900), 1 part of aluminum alkylacetoacetate diisopropylate (aluminum chelate M), and semi-calcined hydrotalcite 200 parts of (DHT-4C) were dispersed with three rolls to obtain a mixture. To the resulting mixture were added 20 parts of glycidyl methacrylate-modified polypropylene-polybutene copolymer (TYP312, 40% toluene solution) and 20 parts of maleic anhydride-modified propylene-butene copolymer (TYP313, 40% toluene solution). , 0.5 parts of an anionic polymerizable amine-based curing agent (TAP) and 170 parts of toluene were blended, and the resulting mixture was uniformly dispersed with a high-speed rotating mixer to obtain a varnish of a resin composition. A sealing sheet was obtained in the same manner as in Example 1 using the obtained varnish.

<Comparative Example 1>
A sealing sheet was prepared in the same manner as in Example 3, except that 1 part of isopropyl tris(dioctylpyrophosphate) titanate (KR38S) was used instead of 1 part of aluminum alkylacetoacetate diisopropylate (aluminum chelate M). Obtained.

<Comparative Example 2>
A sealing sheet was prepared in the same manner as in Example 1, except that 1.5 parts of zirconium stearate (Orgatics ZC320) was used instead of 1.5 parts of aluminum alkylacetoacetate diisopropylate (aluminum chelate M). Obtained.

<Comparative Example 3>
A sealing sheet was obtained in the same manner as in Example 1, except that aluminum alkylacetoacetate diisopropylate (aluminum chelate M) was not added.

<Comparative Example 4>
For sealing, in the same manner as in Example 6, except that aluminum alkylacetoacetate diisopropylate (aluminum chelate M) was not added and the amount of semi-calcined hydrotalcite (DHT-4C) was 100 parts. got a sheet.

<Measurement method/evaluation method>
Various measurement methods and evaluation methods are described below.

<Evaluation of adhesiveness>
The cover film of the sealing sheet (cut into a length of 50 mm and a width of 20 mm) prepared in Examples and Comparative Examples was peeled off, and the resin composition layer was applied to a batch-type vacuum laminator (manufactured by Nichigo-Morton, V-160 ) was used to laminate an aluminum foil/PET composite film “PET Tsuki AL1N30” (aluminum foil: 30 μm, PET: 25 μm: manufactured by Toyo Aluminum Sales Co., Ltd.) having a length of 100 mm and a width of 25 mm. Lamination was performed under the conditions of a temperature of 80° C., a time of 300 seconds, and a pressure of 0.3 MPa. Then, the PET film was peeled off, and a glass plate (length 76 mm, width 26 mm, thickness 1.2 mm, microslide glass) was further laminated on the exposed resin composition layer under the same conditions as above. The obtained laminate was peeled off at a pulling speed of 300 mm/min in a direction of 180 degrees with respect to the length direction of the aluminum foil/PET composite film, and the adhesiveness was measured by the peel strength.
Good (○): Peel strength is 0.2 kgf/cm or more Poor (×): Peel strength is less than 0.2 kgf/cm

<Evaluation of transparency>
The encapsulating sheets prepared in Examples and Comparative Examples were cut into a length of 50 mm and a width of 20 mm, the cover film was peeled off, and the resin composition layer was applied to a glass plate (length 76 mm, width 26 mm and thickness 1.2 mm). (Matsunami Glass Industry Co., Ltd. white slide glass S1112 edge-polished No. 2) was laminated using a batch-type vacuum laminator (Nichigo-Morton, V-160) to obtain a sample for evaluation. The lamination conditions were a temperature of 80° C., a pressure reduction time of 30 seconds, and a pressure of 0.3 MPa for 30 seconds. Peel off the PET film of the sealing sheet, use a haze meter manufactured by Suga Test Instruments Co., Ltd., measure the haze of the evaluation sample (thickness 20 μm) with air as a reference with D65 light, and measure the transparency according to the following criteria. evaluated.
Good (○): Haze is less than 3.5% Poor (×): Haze is 3.5% or more

<Evaluation of moisture permeability resistance>
In each of the examples and comparative examples, the aluminum foil/PET composite film "PET Tsuki AL1N30" (aluminum foil: 30 µm, PET: 25 µm, Tokai Toyo A sealing sheet was obtained in the same manner as in each example and comparative example, except for using Aluminum Distributor's trade name).

Using non-alkali glass deposited with calcium as a model for the light emitting surface of the organic EL device, the moisture permeability resistance of each sealing sheet was evaluated by measuring the light emitting area reduction start time of the organic EL device (calcium ( Ca) Test). A 50 mm×50 mm square non-alkali glass was washed with boiled isopropyl alcohol for 5 minutes and dried at 150° C. for 30 minutes or more. Using the glass and using a mask with a distance of 3 mm from the edge, calcium (purity 99.8%) was evaporated (thickness 300 nm). After heating a sealing sheet having the same resin composition layer as in each example and comparative example at 130° C. for 1 hour in a glove box, alkali-free glass deposited with calcium was placed in a glove box using a thermal laminator (manufactured by Fujipla Co., Ltd.). A laminated body (evaluation sample) was prepared by laminating each sheet for sealing with a lamination packer DAiSY A4 (LPD2325).

When calcium comes into contact with water, it becomes calcium oxide, which turns from white to transparent. Therefore, the penetration of water into the evaluation sample can be evaluated by measuring the distance (mm) from the edge of the evaluation sample to the white calcium. Therefore, an evaluation sample containing calcium was used as a model for the light-emitting surface of the organic EL device.

First, the distance of deposited calcium from the edge of the sample for evaluation was measured by Mitutoyo's Measuring Microscope MF-U, and this value was used as the initial value. Next, the evaluation sample is left for a certain period of time in a small environmental tester (Espec SH-222) set at a temperature of 85 ° C. and 85% RH, and at regular intervals, from the end of the evaluation sample to calcium. distance was measured. Fick's diffusion formula below:

(Wherein, X represents the distance (mm) from the end of the evaluation sample to the calcium, t represents the time (hr) for the evaluation sample to stand still in the small environmental tester, and K represents the constant of proportionality. show.)
Calculate the proportionality constant K by drawing a theoretical curve using the least squares method from the "distance from the end of the evaluation sample to calcium" and "the time the evaluation sample was left standing in the small environmental tester". bottom. Using the calculated K, the time at which X=2.6 mm was calculated as the emission area reduction start time. The higher the resistance to moisture permeation, the slower the penetration speed of moisture, and the longer the light emitting area reduction start time.
Good (○): 250 hr or more Poor (×): Less than 250 hr

The results in Table 1 show that the sealing sheets of Examples 1 to 6 are excellent in moisture permeation resistance as well as adhesiveness and transparency. On the other hand, the sealing sheets of Comparative Examples 1 and 3 have excellent adhesiveness but poor transparency, and the sealing sheet of Comparative Example 2 has excellent moisture permeability resistance and transparency, but poor adhesiveness. I know it's low. Furthermore, it can be seen that the sealing sheet of Comparative Example 4 is excellent in adhesiveness and transparency, but inferior in moisture permeation resistance.

The encapsulating resin composition of the present invention is excellent in adhesiveness and transparency in addition to moisture permeation resistance, so that it can be suitably used for encapsulating electronic devices, particularly electronic devices such as organic EL devices and solar cells. can be done.

Claims (11)

(A) polyolefin resin;
(B) a hygroscopic filler;
(C) a metal complex; and (D) a sealing resin composition containing a tackifier, wherein (A) the polyolefin resin comprises a polyolefin resin having an acid anhydride group and/or an epoxy group; The content of (B) the hygroscopic filler is more than 45% by mass with respect to 100% by mass of non-volatile components in the sealing resin composition, and the (C) metal complex has the general formula (1) :

(In the formula,
M represents aluminum or zirconium,
R ₁ and R ₃ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, or represents an optionally substituted aralkyl group,
R ₂ is a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, or a substituted represents an aryl group that may be substituted, or an aralkyl group that may have a substituent,
X represents a monodentate ligand whose coordinating atom is an oxygen atom;
The solid line between the oxygen atom (O) and M in [ ] represents a covalent bond,
The dashed line between the oxygen atom (O) and M in [ ] represents a coordinate bond, and
m is an integer of 3 or 4, n is an integer of 1 to 3, and m>n. )
A sealing resin composition which is a metal complex represented by 2. The encapsulating resin composition according to claim 1, wherein (B) the hygroscopic filler is semi-calcined hydrotalcite. 3. The encapsulating resin composition according to claim 1, wherein (A) the polyolefin resin comprises a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. (A) The resin composition for sealing according to any one of claims 1 to 3 , wherein the polyolefin resin comprises a reaction product of a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group. . The encapsulating resin composition according to any one of claims 1 to 4 , wherein the content of (C) the metal complex is 0.1 to 5% by mass based on 100% by mass of non-volatile components in the resin composition. The encapsulating resin composition according to any one of claims 1 to 5 , wherein the content of (D) the tackifier is 5 to 40% by mass with respect to 100% by mass of non-volatile components in the resin composition. The encapsulating resin composition according to any one of claims 1 to 6 , which is used for encapsulating electronic devices. 8. The encapsulating resin composition according to claim 7 , wherein the electronic device is an organic EL device or a solar cell. A sealing sheet comprising a support and a layer of the resin composition according to any one of claims 1 to 8 formed on the support. An electronic device sealed with the sealing resin composition according to any one of claims 1 to 6 . 11. The electronic device according to claim 10 , wherein the electronic device is an organic EL device or a solar cell.