TW201730271A - Sealing composition - Google Patents

Abstract

Provided is an organic EL element sealing composition which is to be used as a dam material when sealing an organic EL element using the dam-and-fill method, and capable of protecting the organic EL element by efficiently forming a dam that exhibits moisture-proofing properties and low outgassing, and avoids directly exposing the organic EL element to UV light. This organic EL element sealing composition is to be used as a dam material when sealing an organic EL element using the dam-and-fill method, and contains a component (A), a component (B), a component (C), and a component (D), wherein: the component (A) is a cationic curable compound having, in each molecule thereof, two or more groups selected from an alicyclic epoxy group, an oxetane ring-containing group, an episulfide group, and a vinyl ether group; the component (B) is a photo-cationic polymerization initiator; the component (C) is one or more types of compounds selected from an N-glycidyl compound, an N-vinyl compound, and an N-aryl compound; and the component (D) is an inorganic filler.

Description

Package composition

The present invention relates to a package composition which can be packaged without damaging the organic EL element to prevent deterioration due to moisture. The present application claims priority from Japanese Patent Application No. 2015-239493, filed on Jan.

An organic electroluminescence (hereinafter referred to as "organic EL" element) has a structure in which a light-emitting layer is sandwiched between a pair of counter electrodes, and electrons are injected from one electrode to the other. The electrode is injected into the hole. When the injected electrons and holes are bonded in the light-emitting layer, light is generated. There are two types of light extraction methods of the organic EL element: a top emission type and a bottom emission type. The top emission type has a large aperture ratio and is excellent in light extraction efficiency. Preferably. An organic EL device including an organic EL element is expected to be a full-color flat panel display or a replacement LED because of its high impact resistance, high visibility, and illuminating color.

However, organic EL elements are more susceptible to moisture than other electronic parts, and the oxidization characteristics are remarkably lowered due to oxidation of the electrodes or modification of organic substances due to moisture immersed in the organic EL elements. Low problem. As a method for solving this problem, a method of encapsulating (or coating) a resin having excellent moisture resistance around the periphery of the organic EL element is known.

In the above-described encapsulation method, it is known that the periphery of the organic EL element formed on the substrate is filled with a package composition having a property of being cured by UV irradiation, and then the composition for encapsulation is cured. A method (1) of encapsulating; or coating a lid having the above-described properties on a lid, irradiating UV, and bonding the substrate (2) to a substrate on which an organic EL element has been formed.

In the above method (1), there is a problem that the organic EL element is directly exposed to UV to lower the light-emitting characteristics. In addition, in the case where the color filter is disposed on the upper portion of the organic EL element in order to form the organic EL device having high contrast, since the color filter is shielded from UV, the hardening of the package composition is insufficient. problem.

On the other hand, in the above method (2), it is possible to prevent the organic EL element from being directly exposed to UV and the light-emitting property is lowered, but the curing of the package composition is rapidly performed by UV irradiation, and the bonding industry is carried out. It becomes difficult and the fit becomes difficult, and there is a problem that the yield is lowered.

Patent Document 1 describes a package composition containing an epoxy compound, a polymerization initiator, a crown ether or a polyether as a hardening retarder, and has a UV shielding even after UV irradiation. When the reaction is carried out and the curing is completed, when the composition is used in the above method (2), deterioration of the organic EL element due to UV can be suppressed and encapsulation can be performed. However, the crown ether or the polyether is decomposed by cations to generate outgas, and there is a problem that the organic EL element is deteriorated by the exhaust gas.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4384509

Therefore, an object of the present invention is to provide a composition for encapsulating an organic EL element, which is a composition used as a coffin when encapsulating an organic EL element by a dam and fill method, which may not have an organic EL The element is directly exposed to UV to efficiently form a crucible having low exhaust gas and moisture resistance to protect the organic EL element.

As a result of intensive review to solve the above problems, the present inventors have found that an N-glycidyl compound, an N-vinyl compound, and an N-allyl group selected from the group consisting of a cation which is generated from a photocationic polymerization initiator are weakly basic. At least one compound (hereinafter sometimes referred to as "N-glycidyl compound" or the like) of the compound has "capturing a cation generated from a photocationic polymerization initiator by UV irradiation, and suppresses progress of cationic polymerization. When the heat treatment is performed, the cation is released to cause the cationic polymerization to proceed. The N-glycidyl compound or the like does not cause the exhaust gas; and the encapsulating composition containing the N-glycidyl compound or the like is included. By adjusting the timing of the UV irradiation and the heat treatment, the operable time can be freely controlled, and the package composition is irradiated with UV, and then bonded to the organic EL element, and then subjected to heat treatment to obtain an organic EL. The component is not directly exposed to UV and the bonding does not become difficult The package can encapsulate the organic EL element with a cured product having low exhaust and moisture resistance. The present invention has been completed based on such knowledge.

That is, the present invention provides a composition for encapsulating an organic electroluminescence device, which is a composition used as a coffin when encapsulating an organic electroluminescence device by a cofferdam filling method, and contains the following component (A) , component (B), component (C), and component (D).

Component (A): one of two molecules selected from the group consisting of an alicyclic epoxy group, an oxetane ring-containing group, an episulfide group, and a vinyl ether group. a cationically curable compound of two or more kinds (excluding a compound equivalent to the component (C))

Ingredient (B): Photocationic polymerization initiator

Component (C): at least one compound selected from the group consisting of an N-glycidyl compound, an N-vinyl compound, and an N-allyl compound (excluding N-glycidyl isocyanurate)

Ingredient (D): Inorganic filler

Furthermore, the present invention provides the composition for encapsulating an organic electroluminescence device according to the above, wherein the component (C) is a compound represented by the following formula (c-1)

(In the formula (c-1), R ^a represents a single bond to form the via structure from a hydrocarbon, the heterocyclic ring structure of formula, or a hydrocarbon group with a heterocyclic structure of formula t removing hydrogen atoms; R ^b represents a group selected a hydrogen atom, or a hydrocarbon group, a heterocyclic group, and the group bonded via a single bond; R ^c represents at least one selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group; 1 or 2, t represents an integer of 1 or more; when t is 2 or more, the bases of 2 or more square brackets may be the same or different), and/or the following formula (c-2) Compound

(In the formula (c-2), the ring Z represents a heterocyclic ring containing a nitrogen atom, and R ^c represents at least one selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group; and u represents an integer of 1 or more; When u is 2 or more, two or more nitrogen atoms contained in the ring Z may be directly bonded or may be bonded via another atom.

Furthermore, the present invention provides the composition for encapsulating an organic electroluminescence device according to the above aspect, wherein the component (C) is contained in an amount of 0.05 to 3 parts by weight based on 1 part by weight of the component (B).

Moreover, the present invention provides the composition for encapsulating an organic electroluminescence device as described above, which further contains the following component (E).

Component (E): a compound having one or more glycidyl ether groups in one molecule (excluding a compound corresponding to the component (A) and the component (C))

Further, the present invention provides the composition for encapsulating an organic electroluminescence device according to the above aspect, wherein the component (D) is an inorganic filler having an average particle diameter of 0.001 to 30 μm.

Moreover, the present invention provides the composition for encapsulating an organic electroluminescence device according to the above aspect, wherein the component (D) is a flat inorganic filler.

Moreover, the present invention provides an organic electroluminescent device A method for producing an organic electroluminescence device comprising the following 1 to 3 is provided.

1: The above-described composition for encapsulating an organic electroluminescence device is coated on a lid to form a crucible

2: Apply light to the cockroach

3: A substrate having an organic electroluminescence element is attached to a cover having a ruthenium after light irradiation, and heat treatment is performed

Moreover, the present invention provides an organic electroluminescence device having a structure in which a crucible containing a cured product of the above-described composition for encapsulating an organic electroluminescence device is disposed so as to surround the periphery of the organic electroluminescence device.

That is, the present invention relates to the following items.

[1] A composition for encapsulating an organic electroluminescence device, which is a composition used as a coffin when encapsulating an organic electroluminescence device by a cofferdam filling method, and contains the following components (A) and components (B) ), component (C), component (D): component (A): two or more selected from the group consisting of an alicyclic epoxy group, an oxetane ring-containing group, an episulfide group, and ethylene. a cationically curable compound of one or more kinds of the group of the ether group (excluding the compound corresponding to the component (C)); a component (B): a photocationic polymerization initiator; and a component (C): selected from N - at least one of a glycidyl compound, an N-vinyl compound, and an N-allyl compound (excluding N-glycidyl isocyanurate); component (D): an inorganic filler.

[2] The composition for encapsulating an organic electroluminescence device according to [1], wherein the component (A) is selected from (3,4,3',4'-diepoxy)bicyclohexane, bis ( 3,4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohex-1-yl)ethane, 2,2-double (3,4-epoxycyclohex-1-yl)propane, 1,2-bis(3,4-epoxycyclohex-1-yl)ethane, and formula (1) to (10) At least one compound of the compounds shown.

[3] The composition for encapsulating an organic electroluminescence device according to [1], wherein the component (A) is (3,4,3',4'-diepoxy)bicyclohexane and/or bis ( 3,4-Epoxycyclohexylmethyl)ether.

[4] The composition for encapsulating an organic electroluminescence device according to any one of [1], wherein the content of the component (A) is a curable compound contained in the composition for encapsulating the organic electroluminescence device. 15 to 50% by weight of the total amount (100% by weight).

[5] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [4] wherein the content of the component (B) is 100 parts by weight of the composition for encapsulating the organic electroluminescence device. The curable compound contained is 0.05 to 4 parts by weight.

[6] The composition for encapsulating an organic electroluminescence device according to any one of [1], wherein the component (C) is a compound represented by the formula (c-1) and/or a formula (c-). 2) The compound shown.

[7] The composition for encapsulating an organic electroluminescence device according to [6], wherein the compound represented by the formula (c-1) is selected from the group consisting of 4,4'-methylenebis(N,N-bi-diverted water). Glycerylaniline), N,N,N',N'-tetraglycidyl-1,3-benzenedi(methylamine), N,N,N',N'-tetraglycidyl-1,3- At least one of cyclohexane bis(methylamine) and N,N-bisglycidyl-4-glycidoxyaniline Compound.

[8] The composition for encapsulating an organic electroluminescence device according to [6], wherein the compound represented by the formula (c-2) is 1,3,4,6-tetraglycidylacetylene urea and/or 1, 3,4,6-tetraallylacetylene urea.

The composition for encapsulating an organic electroluminescence device according to any one of the above aspects, wherein the component (B) contains 0.05 to 3 parts by weight based on 1 part by weight of the component (B). .

[10] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [9] further comprising the following component (E): Component (E): a compound having one or more glycidyl ether groups in one molecule (excluding a compound corresponding to the component (A) and the component (C)).

[11] The composition for encapsulating an organic electroluminescence device according to [10], wherein the component (E) is selected from the group consisting of an aliphatic glycidyl ether epoxy compound, an aromatic glycidyl ether epoxy compound, and At least one compound of the alicyclic glycidyl ether epoxy compound.

[12] The composition for encapsulating an organic electroluminescence device according to the above [10], wherein the component (E) is a fragrance having one or more glycidyl ether groups in one molecule and having no ester bond or polyether structure. A family of glycidyl ether epoxy compounds.

[13] The composition for encapsulating an organic electroluminescence device according to any one of [10], wherein the content of the component (E) is a curable compound contained in the composition for encapsulating the organic electroluminescence device. 10 to 90% by weight of the total amount (100% by weight).

[14] The composition for encapsulating an organic electroluminescence device according to any one of [10] to [13] wherein the total content of the component (A) and the component (E) is It is 70% by weight or more of the total amount (100% by weight) of the curable compound contained in the composition for encapsulating the organic electroluminescence element.

[15] The composition for encapsulating an organic electroluminescence device according to any one of [10], wherein the alicyclic epoxy compound and the aromatic glycidyl ether ring represented by the formula (a) The total content of the oxygen compound is 70% by weight or more based on the total amount (100% by weight) of the curable compound contained in the composition for encapsulating the organic electroluminescence device.

[16] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [15] wherein the component (D) is an inorganic filler having an average particle diameter of 0.001 to 30 μm.

[17] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [16] wherein the component (D) is a flat inorganic filler.

[18] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [17] wherein the content of the component (D) is 100 parts by weight of the composition for encapsulating the organic electroluminescence device. The curable compound contained is 30 to 70 parts by weight.

[19] The composition for encapsulating an organic electroluminescence device according to any one of [1] to [18], wherein the viscosity (25 ° C, shear rate: 20 (1/s)) is 10,000 to 2,000,000. mPa‧s.

[20] A method of producing an organic electroluminescence device, comprising: an organic electroluminescence device encapsulation step comprising the following 1 to 3:1: coating on a cover such as any one of [1] to [19] The composition for encapsulating the organic electroluminescence device is formed to form ruthenium; 2: illuminating the ruthenium; and 3: arranging the organic electroconductor on the cover having the ruthenium after the light irradiation The substrate of the light-emitting element is subjected to a heat treatment.

[21] An organic electroluminescence device having a configuration in which a crucible is disposed around a periphery of an organic electroluminescence device, the crucible comprising the organic electro-electrode according to any one of [1] to [19] A cured product of a composition for light-emitting element encapsulation.

[22] The organic electroluminescence device according to [21], wherein the cured product of the composition for encapsulating the organic electroluminescence device has a moisture permeability of 150 g/m ² ‧day ‧ atm or less.

[23] The organic electroluminescence device according to [21], wherein the amount of the cured product of the composition for encapsulating the organic electroluminescence device is 90 ppm or less.

According to the composition for organic EL device encapsulation of the present invention, even if UV is applied to the crucible formed by applying the coating to the lid, the curing can be suppressed until the heat treatment is performed, even if the organic EL element is provided. The bonding of the substrate is delayed, and the adhesion is not lost, making the bonding difficult. Further, by performing heat treatment after bonding, curing can be performed, and the organic EL element can be packaged without directly exposing it to UV. Moreover, the composition for organic EL element encapsulation of the present invention can form a cured product which is excellent in moisture resistance and low in venting property, and can prevent deterioration of the organic EL element due to exhaust gas.

Therefore, the composition for organic EL element encapsulation of the present invention is suitably used as a material for packaging an organic EL element (particularly, a top emission type organic EL element) by a cofferdam filling method.

Moreover, the composition for encapsulating an organic EL device of the present invention is used as a borrowing The organic EL device encapsulated by the coffin in the package filling method has excellent light-emitting characteristics, long life, and high reliability.

1‧‧‧ Cover

2‧‧‧堰

3‧‧‧Distributor

4‧‧‧Filling

5‧‧‧Packaging agent layer

6‧‧‧ cathode

7‧‧‧Lighting layer

8‧‧‧Anode

9‧‧‧Substrate

[Fig. 1] is a schematic view showing an example of a method of producing an organic EL device using the composition for organic EL device encapsulation of the present invention.

[Formation of the Invention]

[Composition for organic EL device packaging]

The composition for encapsulating an organic EL device of the present invention (hereinafter sometimes referred to as "packaging composition") contains the following components (A), (B), (C), and (D): components ( A): one or more of two or more selected from the group consisting of an alicyclic epoxy group, an oxetane group-containing group, an episulfide group, and a vinyl ether group in one molecule. a cationically curable compound (excluding a compound corresponding to the component (C)); a component (B): a photocationic polymerization initiator; a component (C): selected from the group consisting of an N-glycidyl compound, an N-vinyl compound, and N - at least one compound of the allyl compound (excluding N-glycidyl isocyanurate); component (D): an inorganic filler.

In the present specification, the alicyclic epoxy group is a group in which two carbon atoms adjacent to each other of the alicyclic ring are bonded to one oxygen atom, and examples thereof include cyclohexene. Oxide).

(ingredient (A))

The component (A) in the present invention is one which has two or more selected from the group consisting of an alicyclic epoxy group, an oxetane ring-containing group, an episulfide group, and a vinyl ether group in one molecule. Or a cationically curable compound of two or more types, wherein a compound corresponding to the component (C) is excluded.

The compound represented by the following formula (a) is exemplified as a compound having two or more alicyclic epoxy groups in the above-mentioned one molecule (hereinafter referred to as "alicyclic epoxy compound").

In the above formula (a), R ¹ to R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent.

Examples of the halogen atom in R ¹ to R ¹⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

To R ¹ ~ R ¹⁸ in terms of the hydrocarbon group include a hydrocarbon group such as an aliphatic, alicyclic hydrocarbon group, an aromatic hydrocarbon group, and these two or more single bond to form a group of the via.

The above aliphatic hydrocarbon group may, for example, be a C _1-20 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group or a dodecyl group ( Preferred is C _1-10 alkyl, particularly preferably C _1-4 alkyl); vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2 a C _2-20 alkenyl group such as butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl or 5-hexenyl (preferably) It is a C _2-10 alkenyl group, particularly preferably C _2-4 alkenyl); ethynyl, propynyl C _2-20 alkynyl groups (preferably C _2-10 alkynyl group, particularly preferably C _2-4 Alkynyl) and the like.

Examples of the above alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclododecyl group; a C _3-12 ring such as a cyclohexenyl group; Alkenyl; C _4-15 bridged cyclic hydrocarbon group such as bicycloheptyl or bicycloheptenyl.

The aromatic hydrocarbon group may, for example, be a C _6-14 aryl group such as a phenyl group or a naphthyl group (preferably a C _6-10 aryl group).

In addition, the above-mentioned group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group via a single bond may be a C _3-12 cycloalkyl group such as a cyclohexylmethyl group. Substituted C _1-20 alkyl; C _3-12 cycloalkyl substituted by C _1-20 alkyl such as methylcyclohexyl; C _7-18 aralkyl such as benzyl or phenethyl (especially C _{7 -10} aralkyl); Gui the basal substituted by C _6-14 aryl group, etc. C _2-20 alkenyl group; tolyl group substituted by C _1-20 alkyl group of C _6-14 aryl group; a styryl group and the like via C _2-20 alkenyl substituted C _6-14 aryl and the like.

Examples of the hydrocarbon group which may contain an oxygen atom or a halogen atom in R ¹ to R ¹⁸ include a group in which at least one hydrogen atom of the above hydrocarbon group is substituted with a group having an oxygen atom or a halogen atom. The above-mentioned group having an oxygen atom may, for example, be a hydroxyl group; a hydroperoxy group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group or the like C _{1- a} C _2-10 alkenyloxy group; an alkenyloxy group; a substituent having a C _1-10 alkyl group, a C _2-10 alkenyl group, a halogen atom, and a C _1-10 alkoxy group; a C _6-14 aryloxy group (for example, a tolyloxy group, a naphthyloxy group, etc.); a C _7-18 aralkyloxy group such as a benzyloxy group or a phenethyloxy group; an ethoxy group, a propyloxy group, (meth) Bing Xixi, benzyloxy, acyl group, C _1-10 acyl group and the like; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, etc. the C _1-10 alkoxycarbonyl group; may have selected a C _6-14 aryloxycarbonyl group having a substituent of a C _1-10 alkyl group, a C _2-10 alkenyl group, a halogen atom, and a C _1-10 alkoxy group (for example, phenoxycarbonyl, tolyloxycarbonyl, naphthyloxy) a carbonyl group or the like; a C _7-18 aralkyloxycarbonyl group such as a benzyloxycarbonyl group; an epoxy group-containing group such as a glycidyloxy group; an oxetanyl group such as an ethyloxetanyl group; acyl, acyl propyl, benzyl, acyl C _1-10 acyl and the like; isocyanato group; a sulfonic group; carbamoyl acyl; oxo; Etc., via two or more to form a single bond or C _1-10 alkylene group of keys and the like.

Examples of the alkoxy group in R ¹ to R ¹⁸ include a C _1-10 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group or an isobutoxy group. .

Examples of the substituent which may have an alkoxy group include a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, and a C _1-10 fluorene group. Oxyl, fluorenyl, C _1-10 alkylthio, C _2-10 arylthio, C _6-14 arylthio, C _7-18 aralkylthio, carboxy, C _1-10 alkoxycarbonyl, C _6-14 aryloxycarbonyl, C _7-18 aralkyloxycarbonyl, amine, mono or di C _1-10 alkylamino, C _1-10 fluorenylamino, epoxy group-containing, An oxetanyl group, a C _1-10 fluorenyl group, a pendant oxy group, and the like which are bonded to each other by a single bond or a C _1-10 alkyl group.

In the above formula (a), X represents a single bond or a linking group (a divalent group having one or more atoms). The above-mentioned linking group may, for example, be a divalent hydrocarbon group or a part or all of an epoxidized alkenyl group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amidino group, and/or a carbon-carbon double bond. These multiple Connected to the base, etc.

The divalent hydrocarbon group may, for example, be a linear or branched chain alkyl group having a carbon number of 1 to 18 or a divalent alicyclic hydrocarbon group. Examples of the linear or branched chain alkyl group having a carbon number of 1 to 18 include, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylidene group, and a propyl group. , trimethylene and so on. The above-mentioned divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclohexylene group, or a 1,3- A cycloalkyl group (including a cycloalkylene group), etc., such as a cyclohexyl group, a 1,4-cyclohexylene group, or a cyclohexylene group.

Examples of the alkenyl group in the epoxidized alkenyl group (sometimes referred to as "epoxidized alkenyl group") of one or all of the above carbon-carbon double bonds include, for example, a vinyl group and a propylene group. a linear chain of 2 to 8 carbon atoms such as a 1-butenyl group, a 2-butenbutenyl group, a butadienyl group, a pentenyl group, a hexenylene group, a heptenyl group, and an octenyl group. An alkenyl group such as a chain or a branched chain. In particular, in the case of the above epoxidized alkenyl group, all of the epoxidized alkenyl groups of the carbon-carbon double bond are preferred, and more preferably the carbon-carbon double bond is epoxidized to have a carbon number of 2 to 4 The alkenyl group.

With respect to the above-mentioned linking group in X, a linking group containing an oxygen atom is particularly preferable, and specific examples thereof include -CO-, -O-CO-O-, -COO-, -O-, -CONH. And a plurality of such groups are bonded to each other; one or two or more such groups are bonded to one or more of the above-mentioned divalent hydrocarbon groups.

Representative examples of the alicyclic epoxy compound represented by the above formula (a) include, for example, (3,4,3',4'-diepoxy)bicyclohexane, bis (3,4). -Epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohex-1-yl)ethane, 2,2-bis (3, 4-epoxycyclohex-1-yl)propane, 1,2-bis(3,4-epoxycyclohex-1-yl)ethane, or the following formulas (1) to (10) Compounds and the like. Further, L in the following formula (5) is an alkylene group having 1 to 8 carbon atoms, and a linear or branched chain alkyl group having 1 to 3 carbon atoms is preferred. In the following formulas (5), (7), (9), and (10), n ¹ to n ⁸ are the same or different, and represent an integer of 1 to 30.

In the case of an alicyclic epoxy compound, from the viewpoint of obtaining a cured product having excellent hardenability, heat resistance (high glass transition temperature), low shrinkage, or low linear expansion property, it is used (3, 4, 3',4'-Dioctyloxy)bicyclohexane and/or bis(3,4-epoxycyclohexylmethyl)ether are preferred. From the viewpoint of obtaining a cured product excellent in moisture resistance, (3,4,3',4'-diepoxy)bicyclohexane is preferred.

The compound having two or more oxetane ring-containing groups in the above one molecule may, for example, be 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl group. Benzene, bis{[1-ethyl(3-oxetanyl)]methyl}ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl Cyclohexane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 3-ethyl-3{[(3-ethyl Oxetane-3-yl)methoxy]methyl}oxetane, phenol novolac type oxetane, and the like. For example, the trade name "ETERNACOLL OXBP" can be used (Ube Hiroshi ( Commercial products such as shares).

Examples of the compound having two or more episulfide groups in the above-mentioned one molecule include, for example, 1,3-bis(β-cyclothiopropylthio)cyclohexane and 1,3-bis(β-ring). Thiopropylpropylthiomethyl)cyclohexane, bis[4-(β-cyclothiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-cyclothiopropylthio) ring Hexyl]propane, bis[4-(β-cyclothiopropylthio)cyclohexyl] sulfide, 2,5-bis(β-cyclothiopropylthio)-1,4-dithiazide (dithiane), 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiazide An episulfide compound having an alicyclic ring; 1,3-bis(β-cyclothiopropylthio)benzene, 1,3-bis(β-cyclothiopropylthiomethyl)benzene, bis[4- (β-Cyclothiopropylthio)phenyl]methane, 2,2-bis[4-(β-cyclothiopropylthio)phenyl]propane, bis[4-(β-cyclothiopropyl sulfide) Phenyl] thioether, bis[4-(β-cyclothiopropylthio)phenyl]sulfinium, 4,4-bis(β-cyclothiopropylthio)biphenyl, etc. An episulfide compound having an aromatic ring; 2-(2-β-cyclothiopropylthioethylthio)-1,3-bis(β-cyclothiopropylthio)propane, 1,2-double [ (2-β-cyclothiopropylthioethyl)thio]-3-(β-cyclothiopropylthio)propane, hydrazine (β-cyclothiopropylthiomethyl)methane, 1,1 , an alkylsulfide-type episulfide compound such as 1-paran (β-cyclothiopropylthiomethyl)propane; 9,9-bis{4-[2-(2,3-cyclothiopropoxy) Ethoxy]phenyl}indole, 9,9-bis{4-[2-(2,3-cyclothiopropoxy)ethoxy]-3-methylphenyl}anthracene, 9,9 -Bis{4-[2-(2,3-Cyclosulfanyloxy)ethoxy]-3,5-dimethylphenyl}anthracene, 9,9-double {4-[2-(2 ,3-cyclothiopropoxy)ethoxy]-3-phenylphenyl}indole, 9,9-bis{6-[2-(2,3-cyclothiopropoxy)ethoxy ] Cyclone sulfide having an anthracene skeleton such as -2-naphthyl}anthracene, 9,9-bis{5-[2-(2,3-cyclothiopropoxy)ethoxy]-1-naphthalenyl}anthracene Compounds, etc.

With respect to the above one molecule having two or more vinyl ether groups Examples of the compound include a cyclic ether type vinyl ether compound such as isosorbide divinyl ether or oxynordecene divinyl ether (having an oxirane ring and an oxirane ring). a vinyl ether compound of a cyclic ether group such as a butane ring or an oxolane ring; an aryl divinyl ether compound such as hydroquinone divinyl ether; and a 1,4-butanediol divinyl group. a vinyl ether compound having a chain hydrocarbon group such as ether; a chain ether type vinyl ether compound such as triethylene glycol divinyl ether; a ring having cyclohexane divinyl ether or cyclohexane dimethanol divinyl ether A vinyl ether compound of a hydrocarbon group.

The component (A) may be used alone or in combination of two or more. The content (mixing amount) of the component (A) in the total amount (100% by weight) of the curable compound contained in the encapsulating composition of the present invention is, for example, about 15 to 50% by weight, preferably 20 to 40% by weight. . When the component (A) is contained in the above range, it is preferable to suppress the progress of the curing when the curing is delayed, and to perform rapid curing after the heat treatment. When the content of the component (A) is less than the above range, it is difficult to obtain a sufficient curing rate even if heat treatment is performed. On the other hand, when the content of the component (A) exceeds the above range, it tends to be difficult to obtain a sufficient hardening retardation effect.

(ingredient (B))

The component (B) in the present invention is a photocationic polymerization initiator which starts a cationic species by irradiation of light and starts a curing reaction of the cationically curable compound. A photocationic polymerization initiator comprising a cationic portion that absorbs light and an anion portion that serves as a source of acid generation.

The photocationic polymerization initiator in the present invention may, for example, be a diazonium salt compound or a phosphonium salt compound. An onium salt compound, a phosphonium salt compound, a selenium salt compound, an oxonium salt compound, an ammonium salt compound, a bromine salt compound, and the like. Among them, the use of the onium salt-based compound is preferred from the viewpoint of forming a cured product excellent in curability.

The cation moiety of the onium salt-based compound may, for example, be an aryl phosphonium ion such as a triphenylphosphonium ion, a diphenyl[4-(phenylthio)phenyl]phosphonium ion or a tris-p-tolylphosphonium ion ( Especially triaryl sulfonium ions).

The anion portion of the photocationic polymerization initiator may, for example, be [(Y) _k B(Phf) _4-k ] ^- (wherein Y represents a phenyl group or a biphenyl group; and Phf represents at least one hydrogen atom) a phenyl group substituted with at least one selected from the group consisting of a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom; k is an integer of 0 to 3), BF ₄ ^- , B(C ₆ F ₅ ) ₄ ^- , PF ₆ ^- , [(Rf) _n PF _6-n ] ^- (Rf: 80% or more of a hydrogen atom substituted by a fluorine atom, n: an integer of 1 to 5), AsF ₆ ^- , SbF ₆ ^- , SbF ₅ OH ^- and so on.

The photocationic polymerization initiator in the present invention may, for example, be 4-(4-biphenylthio)phenyl-4-biphenylphenyl hydrazine or hydrazine (pentafluorophenyl)borate. Pentafluorophenyl)boronic acid diphenyl[4-(phenylthio)phenyl]anthracene, diphenyl[4-(phenylthio)phenyl]phosphonium hexafluorophosphate, ginseng (pentafluoroethyl)trifluoro 4-(4-biphenylthio)phenyl-4-biphenylphenylphosphonium phosphate, 4-phenylsulfonylphenyldiphenylphosphonium phenyl phenyl pentoxide 4-(pentafluorophenyl)boronic acid [4-(4-biphenylthio)phenyl]-4-biphenylphenyl hydrazine, trade name "Cyracure UVI-6970", "Cyracure UVI-6974", " Cyracure UVI-6990", "Cyracure UVI-950" (above, manufactured by Union Carbide, USA), "Irgacure 250", "Irgacure 261", "Irgacure 264" (above, BASF), "Optomer" SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (above, ADEKA (share) system), "CG-24-61" (manufactured by Ciba Japan), " DAICAT II" (Daicel), "UVAC1590", "UVAC1591" (above, Daicel-Cytec), "CI-2064", "CI-2639", "CI-2624", "CI -2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (above, Japan Soda (share) system), "PI-2074" ( Rhodia, 肆 (pentafluorophenylboronic acid) tolyl cumyl sulfonium salt), "FFC509" (manufactured by 3M Company), "BBI-102", "BBI-101", "BBI-103", MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (above, Midori Kagaku (share) system), "CD-1010" "CD-1011", "CD-1012" (made by Sartomer Inc., USA), "CPI-100P", "CPI-101A" (above, SAN-APRO (share) system). These may be used alone or in combination of two or more.

The amount (or blending amount of the component (B); the total amount thereof in the case of containing two or more kinds), and the cationically curable compound contained in the encapsulating composition of the present invention relative to 100 parts by weight The amount of the two or more kinds thereof is, for example, about 0.05 to 4 parts by weight, preferably 0.2 to 3 parts by weight, particularly preferably 0.5 to 3 parts by weight.

(ingredient (C))

The encapsulating composition of the present invention contains, as component (C), at least one compound selected from the group consisting of an N-glycidyl compound, an N-vinyl compound, and an N-allyl compound. Since the N-glycidyl compound or the like exhibits a weak basicity with respect to the cation generated from the photocationic polymerization initiator, there is The action of the cation generated by the photocationic polymerization initiator by light irradiation is captured, and the effect of suppressing the hardening after the light irradiation to the heat treatment or the hardening delay effect is exhibited. That is, in the present invention, the N-glycidyl compound or the like is a hardening retarder. Further, when heat treatment is performed after light irradiation, the captured cations are released, and the composition for encapsulation is cured. Therefore, by adjusting the timing of performing the heat treatment, the start timing of the hardening can be controlled, and it is possible to prevent the bonding due to the delay of the bonding industry from becoming difficult. The N-glycidyl compound or the like may be used alone or in combination of two or more.

The N-glycidyl compound or the like in the present invention is a compound having a structure in which at least one selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group is bonded to a nitrogen atom of a compound containing a nitrogen atom. For example, it includes a compound represented by the following formula (c-1) or a compound represented by the following formula (c-2).

In the above formula (c-1), R ^a represents ^a group in which t hydrogen atoms are removed from a structural formula of ^a hydrocarbon, a structural formula of a heterocyclic ring, or a structural formula in which a hydrocarbon and a heterocyclic ring are bonded via a single bond. R ^b represents a group selected from a hydrogen atom, a hydrocarbon group, a heterocyclic group, and the like (two or more groups selected from a hydrocarbon group and a heterocyclic group) bonded via a single bond. R ^c represents at least one selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group. s represents 1 or 2, and t represents an integer of 1 or more. In the case where t is 2 or more, the bases in the two or more square brackets may be the same or different.

Further, in the above formula (c-2), the ring Z represents a hetero ring containing a nitrogen atom, and R ^c represents at least one selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group. u represents an integer of 1 or more. When u is 2 or more, two or more nitrogen atoms contained in the ring Z may be directly bonded, or may be bonded via another atom (for example, a carbon atom or the like).

The above R ^a represents a group which removes t hydrogen atoms from a structural formula of ^a hydrocarbon, a structural formula of a heterocyclic ring, or a structural formula in which a hydrocarbon and a heterocyclic ring are bonded via a single bond.

The hydrocarbon includes an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and the like, which are bonded via a single bond.

In the case of the above aliphatic hydrocarbon, a C _1-20 aliphatic hydrocarbon is preferred.

In the case of the aforementioned alicyclic hydrocarbon, a C _3-20 alicyclic hydrocarbon is preferred.

In the case of the above aromatic hydrocarbon, a C _6-14 (especially C _6-10 ) aromatic hydrocarbon is preferred.

The heterocyclic ring includes an aromatic hetero ring and a non-aromatic hetero ring. Examples of such a heterocyclic ring include a 3 to 10 membered ring (preferably 4 to 6) having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in the atoms constituting the ring. Member ring), and these fused rings. Specifically, a hetero ring containing an oxygen atom as a hetero atom (for example, a furan ring, a porphyrin ring or the like, a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a thiophene ring, a thiazole ring, etc.), a hetero ring containing a nitrogen atom as a hetero atom (for example, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring) , triazole ring, isocyanuric ring, pyridine ring, hydrazine Ring, pyrimidine ring, pyridyl Ring, piperidine ring, piperazine Ring, anthracene ring, porphyrin ring, quinoline ring, acridine ring, A pyridine ring, a quinazoline ring, an anthracene ring, etc.).

The above hydrocarbon or heterocyclic ring may bond various substituents [halogen atom, pendant oxy group, hydroxy group, substituted oxy group (for example, C _1-4 alkoxy group, C _6-10 aryloxy group, C _7-16 aryl group). An alkyloxy group, a C _1-4 fluorenyloxy group, a carboxyl group, a substituted oxycarbonyl group (for example, a C _1-4 alkoxycarbonyl group, a C _6-10 aryloxycarbonyl group, a C _7-16 aralkyloxy group) a carbonyl group or the like, a substituted or unsubstituted amine carbenyl group (for example, an amine carbenyl group, an amine carbamidyl group substituted with a C _1-4 alkyl group, an amine carbenyl group substituted with a C _6-10 aryl group), Cyano, nitro, sulfonate, glycidyl ether, etc.]. Further, in the ring of an alicyclic hydrocarbon or an aromatic hydrocarbon, an aromatic or non-aromatic heterocyclic ring may be condensed.

The above R ^a is preferably a valent group having 5 to 20 carbon atoms and containing at least one ring selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and heterocyclic rings.

The hydrocarbon group in R ^b in the above formula includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and two or more of these groups are bonded via a single bond.

In the above aliphatic hydrocarbon group, an aliphatic hydrocarbon group of C _1-20 (= 1 to 20 carbon atoms) is preferable, and for example, about C _1-20 (preferably C _1-10 , particularly preferably C _1-3) alkyl of; about C _2-20 (preferably C _2-10, especially preferably C _2-3) alkenyl group of; about C _2-20 (preferably C _2-10, Laid _Preferably , it is an alkynyl group of C _2-3 ).

The alicyclic hydrocarbon group is preferably a C _3-20 (= 3 to 20 membered) alicyclic hydrocarbon group, and examples thereof include a C _5-20 such as a cyclopentyl group or a cyclohexyl group (preferably C). _3-15 , particularly preferably a C _5-8 ) cycloalkyl group; a cyclopentenyl group, a cyclohexenyl group or the like, about C _3-20 (preferably C _3-15 , particularly preferably C _5-8 ) a cycloalkenyl group; a bridged cyclic hydrocarbon group such as a thiol group; and the like.

The aromatic hydrocarbon group is preferably a C _6-14 (especially C _6-10 ) aromatic hydrocarbon group, and examples thereof include a phenyl group and the like.

The heterocyclic group in R ^b in the above formula is a group in which one hydrogen atom is removed from the structural formula of the hetero ring, and examples of the above heterocyclic ring include the same as the hetero ring in R ^a .

In the above hydrocarbon group or heterocyclic group, various substituents may be bonded in the same manner as the hydrocarbon or heterocyclic ring in R ^a . Further, in the ring of the alicyclic hydrocarbon group or the aromatic hydrocarbon group, an aromatic or non-aromatic heterocyclic ring may be condensed.

The aforementioned s represents 1 or 2, preferably 2.

The above t is an integer of 1 or more, and is, for example, 1 to 4.

Further, the product (s × t) of s and t is, for example, an integer of 1 or more, preferably 2 to 4.

The aforementioned ring Z is a heterocyclic ring containing a nitrogen atom, and examples thereof include a pyrrolidine ring, a piperidine ring, and a piperidine. ring, 5 to 10 member rings (preferably 6 to 8 member rings) such as a porphyrin ring, an imidazole ring or an acetylene urea ring.

The above u is an integer of 1 or more, and is, for example, 1 to 4.

The N-glycidyl compound can be produced, for example, by reacting epichlorohydrin with a compound containing a nitrogen atom. For example, a compound represented by the following formula (c-1-1) can be produced by reacting epichlorohydrin with a compound containing a nitrogen atom represented by the following formula (c-1'), and the following formula ( The compound shown by c-2-1) can be produced by reacting epichlorohydrin with a nitrogen atom-containing compound represented by the following formula (c-2'). Further, in the following formula (c-1'), R ^a , R ^b , s, and t are the same as described above. Further, in the following formula (c-2'), the rings Z and u are the same as described above.

Examples of the nitrogen atom-containing compound represented by the formula (c-1') include a chain such as diethylamine, diethylidenetriamine, triethylidenetetraamine, and tetraethylidenepentamine. Aliphatic amine compound; 4,4'-methylenebis(2-methylcyclohexylamine), a cyclic aliphatic amine compound such as menthene diamine, isophorone diamine, 4,4'-methylene bis(cyclohexylamine) or 1,3-diaminomethylcyclohexane; An aromatic amine compound such as xylene diamine, 2,4,6-glycol (dimethylaminomethyl)phenol, m-phenylenediamine, diaminodiphenylmethane or diaminodiphenylphosphonium.

Examples of the nitrogen atom-containing compound represented by the above formula (c-2') include piperidine and pyrrolidine. Porphyrin N-Aminoethyl Pipe A nitrogen-containing heterocyclic compound such as pyrrole, imidazole or acetylene urea.

The N-vinyl compound or the N-allyl compound can also be produced by a method according to the method for producing the aforementioned N-glycidyl compound. . For example, in addition to the use of vinyl chloride in place of epichlorohydrin in the manufacture of N-vinyl compounds, and the use of allyl chloride in place of epichlorohydrin in the manufacture of N-allyl compounds, the N-glycidyl compound described above may be employed. The same method as the manufacturing method.

Examples of the compound represented by the formula (c-1) include 4,4'-methylenebis(N,N-diglycidylaniline), N,N,N',N'-four. Glycidyl-1,3-benzenedi(methylamine), N,N,N',N'-tetraglycidyl-1,3-cyclohexanedi(methylamine), N,N-bisglycidol Keto-4-glycidyloxyaniline and the like. In the present invention, for example, a commercially available product such as "TETRAD-X" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can be used.

Examples of the compound represented by the formula (c-2) include 1,3,4,6-tetraglycidylacetylene urea, 1,3,4,6-tetraallylacetylene urea, 1,3. -Diallyl-4,6-diglycidyl acetylene urea or the like. In the present invention, for example, commercially available products such as "TG-G", "TA-G", and "DAG-G" (above, Shikoku Kasei Kogyo Co., Ltd.) can be used.

The amount (B) of the component (C) to be used is, for example, 1 part by weight of the component (B) contained in the encapsulating composition of the present invention (in the case where two or more kinds thereof are contained), for example The 0.05 to 3 parts by weight, the upper limit is preferably 2.5 parts by weight, particularly preferably 2.0 parts by weight, most preferably 1.5 parts by weight. The lower limit is preferably 0.1 part by weight, particularly preferably 0.2 part by weight, most preferably 0.3 part by weight. It is preferable to contain the component (C) in the above range in order to obtain a sufficient hardening retardation effect. When the content of the component (C) is less than the above range, it tends to be difficult to obtain a sufficient hardening retardation effect. On the other hand, when the content of the component (C) exceeds the above range, even if heat treatment is performed, it becomes difficult to obtain a sufficient curing rate, and hardening occurs. Bad situation.

(ingredient (D))

The package composition of the present invention contains an inorganic filler as the component (D). Therefore, a cured product having excellent moisture resistance can be obtained.

Examples of the inorganic filler include inorganic oxides such as vermiculite, alumina, zinc oxide, and magnesium oxide; carbonates such as calcium carbonate and magnesium carbonate; calcium citrate, glass beads, talc, clay, mica, and the like. Citrate and the like.

In the present invention, it is preferable to use a citrate such as talc or mica because it has linear responsiveness to the coating pressure at the time of dispensing and is excellent in coatability. The average particle diameter of the inorganic fine particles (by laser diffraction ‧ scattering method (micro-track method)) is, for example, 0.001 to 30 μm, preferably 0.1 to 10 μm.

In addition, the shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape (a true spherical shape, a slightly spherical shape, an elliptical spherical shape, etc.), a polyhedral shape, a rod shape (a columnar shape, a prismatic column shape, etc.), and a flat plate shape. Scales, indefinite shapes, etc. Among them, in order to impart more excellent moisture resistance, it is preferred to use a flat inorganic filler.

The content of the inorganic filler is, for example, about 30 to 70 parts by weight, preferably 40 to 60 parts by weight, particularly preferably 45 to 60 parts by weight, per 100 parts by weight of the curable compound contained in the encapsulating composition. . By containing an inorganic filler in the above range, a cured product having excellent moisture resistance can be obtained. When the content of the inorganic filler exceeds the above range, the viscosity becomes too high, and the coatability tends to decrease. On the other hand, if the content of the inorganic filler is less than the above range, the moisture resistance may be insufficient. condition.

(additive)

The package composition of the present invention may contain one or two or more other components as needed in addition to the above components. Examples of the other components include a curable compound other than the component (A), a conductive material, a polymerization inhibitor, a decane coupling agent, an antioxidant, a photostabilizer, a plasticizer, a leveling agent, and defoaming. Agent, solvent, ultraviolet absorber, ion adsorbent, pigment, phosphor, mold release agent, and the like.

(ingredient (E))

In the component (E), the component (E) may contain one or two or more kinds of curable compounds other than the component (A) (excluding the compound contained in the component (C)).

The curable compound other than the component (A) may, for example, be a cationically curable compound such as a compound having an epoxy group, a compound having a vinyl group, or a compound having an allyl group.

The compound having an epoxy group includes, for example, a compound having one alicyclic epoxy group in one molecule, a compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond, a glycidyl ether epoxy compound, and shrinkage. A glyceride-based epoxy compound or the like.

Examples of the compound having one alicyclic epoxy group in the above molecule include, for example, 1,2; 8,9-diepoxylimene, 1,2-epoxy-4-vinylcyclohexane. Wait.

The compound in which the above epoxy group is directly bonded to the alicyclic ring by a single bond may, for example, be 1,2-epoxy-4-(2) of 2,2-bis(hydroxymethyl)-1-butanol. -oxiranyl oxirane adduct (trade name " EHPE3150", Daicel (share) system, etc.

The glycidyl ether-based epoxy compound may, for example, be an aliphatic group such as epichlorohydrin to 1,6-hexanediol-diglycidyl ether or trimethylolpropane-triglycidyl ether. An aliphatic glycidyl ether epoxy compound obtained by a polyol reaction; a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol E epoxy compound, an o-phenylphenol glycidyl ether, Bisphenol type epoxy compound, phenol novolak type epoxy compound, cresol novolac type epoxy compound, bisphenol A cresol novolak type epoxy compound, naphthalene type epoxy compound, ginsyl methane An aromatic glycidyl ether epoxy compound such as an epoxy compound; a hydrogenated bisphenol A epoxy compound (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane , 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane, and bisphenol A type epoxy compounds such as these polymers Hydrogenated compound), hydrogenated bisphenol F-type epoxy compound (bis[o-,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o-, p-(2,3-epoxy) Propyloxy)cyclohexene Methane, bis[p-, p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy) Cyclohexyl]methane, and the like, hydrogenated bisphenol epoxy compound, hydrogenated phenol novolac epoxy compound, hydrogenated cresol novolac epoxy compound, bisphenol A hydrogenated cresol novolac An alicyclic glycidyl ether epoxy compound obtained by hydrogenating an aromatic glycidyl ether epoxy compound, such as a varnish-type epoxy compound, a hydrogenated naphthalene type epoxy compound, or a hydrogenated phenol-methane type epoxy compound. For example, you can use the trade name "YL-983U" (Mitsubishi Chemical Co., Ltd.), "R1710" (made by Printec), "SY-OPG", and "PEG" (above, Sakamoto Pharmaceutical Industry ( Commercial products such as stocks).

Examples of the compound having a vinyl group include styrene such as styrene, p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene, p-terphenylstyrene or the like. a compound; a nitrogen-vinyl compound such as N-vinylcarbazole or N-vinylpyrrolidone.

Examples of the compound having an allyl group include allyl (meth)acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, and the like.

In the present invention, in the case where the curing rate is slow at room temperature, a compound having an epoxy group (preferably a compound having one or more glycidyl ether groups in one molecule, particularly preferably an aromatic shrinkage) is used. The glyceryl ether-based epoxy compound is preferably an aromatic glycidyl ether epoxy compound having one or more glycidyl ether groups in one molecule and having no ester bond or polyether structure. It is preferable from the viewpoint of the generation of exhaust gas and the effect of making the hardening retardation more stable.

In other words, the component (E) preferably contains one or more compounds having an epoxy group (preferably one or more glycidol in one molecule). The ether group-based compound is particularly preferably an aromatic glycidyl ether epoxy compound, and is preferably an aromatic glycidol having one or more glycidyl ether groups in one molecule and having no ester bond or polyether structure. Alkyl ether epoxy compound) (excluding the compound corresponding to the component (A) and the component (C)).

The content of the component (E) in the total amount (100% by weight) of the curable compound contained in the encapsulating composition of the present invention is, for example, about 10 to 90% by weight, the upper limit is preferably 85% by weight, and particularly preferably 80% by weight. %, the best is 75 the amount%. The lower limit is preferably 20% by weight, particularly preferably 30% by weight, most preferably 50% by weight, and most preferably 60% by weight. It is preferable to contain the component (E) in the above range from the viewpoint of making the hardening retardation stable.

In addition, the total content of the component (A) and the component (E) in the total amount (100% by weight) of the curable compound contained in the encapsulating composition of the present invention is, for example, 70% by weight or more, preferably 80% by weight or more. It is particularly preferably 90% by weight or more. Furthermore, the upper limit is 100% by weight.

Further, an alicyclic epoxy compound (particularly (3,4,3',4'-diepoxy group) in the total amount (100% by weight) of the curable compound contained in the encapsulating composition of the present invention The total content of the compound (for example, an aromatic glycidyl ether epoxy compound) having one or more glycidyl ether groups in one molecule is, for example, 70% by weight or more, preferably 80%. More preferably, the weight is at least 90% by weight. Furthermore, the upper limit is 100% by weight.

The package composition of the present invention can be used by using the component (A), the component (B), the component (C), the component (D), and other components as needed (for example, the component (E)). A mixing machine such as a revolutionary stirring and defoaming device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill is uniformly mixed and produced. Further, the components may be mixed at the same time or may be mixed one by one.

The viscosity of the package composition of the present invention before the light irradiation (25 ° C, shear rate: 20 (1/s)) is, for example, about 10,000 to 2,000,000 mPa·s, preferably 20,000 to 1.5 million mPa. ‧s, especially good for 20,000 to 1 million mPa‧s, best for 50,000 to 800,000 mPa‧s, and excellent for 100,000 to 200,000 mPa‧s.

The package composition of the present invention is cured by performing light irradiation and then performing heat treatment. When light is applied to a coating film having a thickness of 100 μm, it is preferred to irradiate light of 500 mJ/cm ² or more by a mercury lamp or the like. Further, the heat treatment is preferably carried out by an oven or the like at, for example, 40 to 200 ° C (particularly 60 to 180 ° C, preferably 80 to 150 ° C) for 10 to 200 minutes (particularly 30 to 120 minutes).

Since the encapsulating composition of the present invention contains the above component (C) having a cation capturing action, even if light irradiation is performed, the cation generated from the cationic polymerization initiator is captured by the component (C), so that the light is irradiated to the heating. The progress of cationic polymerization can be suppressed until the treatment. After the light irradiation, the cation captured by the component (C) is released by heat treatment, and cationic polymerization of the cationically curable compound is carried out to complete the hardening. That is, the hardening can be arbitrarily controlled by adjusting the timing of performing the heat treatment.

The viscosity (25 ° C, shear rate: 20 (1/s)) immediately after the ultraviolet irradiation (irradiation amount: 2000 mJ/cm ² ) of the composition for encapsulation of the present invention is irradiated with a mercury lamp of 200 W/cm, for example, about 10,000 Å. 5 million mPa‧s, preferably 50,000 to 3 million mPa‧s, and particularly good 100,000 to 2 million mPa‧s.

The viscosity of the coating composition of the present invention after irradiation with ultraviolet rays (irradiation amount: 2000 mJ/cm ² ) at a mercury lamp of 200 W/cm for 30 minutes (25 ° C, shear rate: 20 (1/s)) is, for example, about 10,000. ~10 million mPa‧s, preferably 50,000-7 million mPa‧s, especially 100,000 to 5 million mPa‧s.

The viscosity increase degree of the composition for packaging of the present invention after irradiating ultraviolet rays (irradiation amount: 2000 mJ/cm ² ) with a mercury lamp of 200 W/cm to 30 minutes after the irradiation is, for example, 8 times or less (for example, 1 to 8 times). It is preferably 3 times or less, more preferably 2 times or less, and most preferably 1.5 times or less.

Further, the cured product obtained by the above-described method is low in water vapor permeability (that is, excellent in moisture resistance), and the moisture permeability of the cured product (thickness: 100 μm) is, for example, 150 g/m ² ‧day ‧ atm or less. It is preferably 100 g/m ² ‧day ‧ atm or less, particularly preferably 80 g/m ² ‧day ‧ atm or less, preferably 50 g/m ² ‧ day ‧ atm or less, and preferably less than 20 g/m ² ‧ day ‧ Atm. In addition, the moisture permeability is measured by the value of the moisture permeability of the cured product adjusted to a thickness of 100 μm under the conditions of 60 ° C and 90% RH in accordance with JIS L 1099 and JIS Z 0208.

Moreover, the amount of exhaust gas from the hardening retarder obtained by curing the cured product (60 mg) by the above method is about 90 ppm or less (preferably 70 ppm or less, particularly preferably 50 ppm or less), and exhibits low exhaust gas permeability. Further, the amount of exhaust gas can be measured by headspace GC/MS.

The package composition of the present invention has a hardening retardation, and the curing start period can be arbitrarily adjusted. Therefore, by irradiating the package composition with light and then bonding it to the organic EL element and heating it, the organic EL element can be encapsulated without exposing the organic EL element to UV without causing bonding. Further, the package composition of the present invention can form a cured product having both low venting properties and moisture resistance. Therefore, the package composition of the present invention can be suitably used as a coffin when the organic electroluminescence device is packaged by a bank filling method. When the package composition of the present invention is used, the organic EL element can be protected from moisture or exhaust gas, and deterioration of the organic EL element due to moisture or exhaust gas can be prevented.

[Organic EL device]

The organic EL device of the present invention is a device including an organic EL device. When the organic EL device is packaged using the package composition of the present invention, the ruthenium containing the cured product of the package composition of the present invention is disposed so as to surround the periphery of the organic EL device.

When the encapsulating composition of the present invention is used, the organic EL element (especially the top emission type organic EL element) can be prevented from being deteriorated by light irradiation via the organic EL element encapsulating step including the following 1 to 3, and simultaneously performed. The package can produce an organic EL device with long life and high reliability. Further, the light irradiation and the heat treatment method are as described above.

1: Coating the composition for encapsulation of the present invention on a lid to form a crucible

2: Apply light to the cockroach

3: A cover having an organic EL element is attached to a cover having a light after irradiation, and heat treatment is performed

In the method for producing an organic EL device of the present invention, it is preferable to provide a step of filling a filler into the crucible formed by one after the completion of one of the steps of encapsulating the organic EL device and before being applied to . Further, in the case of the filler, it is preferred to use a curable composition containing the component (B) and the component (C) of the present invention, and particularly, it has the same composition as the encapsulating composition (coffin) of the present invention. The curing retardation effect is not required to directly expose the organic EL element to UV, and it is preferable to use the component (A), the component (B), the component (C), and the optional component (E) in the present invention. (It is preferred to contain the components (A), (B), (C), (E)) in the same ratio as the encapsulating composition of the present invention, and the viscosity (25 ° C, shear rate: 20 (1/s) )) is, for example, a composition of about 10 to 10,000 mPa ‧ s, preferably 20 to 3,000 mPa ‧ s, particularly preferably 30 to 2,500 mPa ‧ s, and most preferably 30 to 1,000 mPa ‧ s.

In other words, in the method for producing an organic EL device of the present invention, it is preferable to have a step of encapsulating an organic EL device comprising the following 1 to 4 (see Fig. 1).

1: Coating the composition for encapsulation of the present invention on the lid (1) to form bismuth (2)

2: filling the foregoing filler (4) in the crucible (2) to form a package layer (5)

3: Light irradiation on the encapsulant layer (5)

4: On the cover (1) having the encapsulant layer (5) after light irradiation, the substrate (9) on which the organic EL elements (6, 7, 8) are provided is bonded and heat-treated

The lid and the substrate are preferably a moisture-proof substrate, and examples thereof include a glass substrate such as soda glass or alkali-free glass; a metal substrate such as stainless steel or aluminum; and a trifluoroethylene. Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), a copolymer of PCTFE and PVDF, a copolymer of PVDF and a polyfluorinated vinyl chloride, and the like, a polyfluorinated ethylene polymer; a cycloolefin resin such as polycarbonate or dicyclopentadiene; a polyester such as polyethylene terephthalate; a resin substrate such as polyethylene or polystyrene; Although the cover and the substrate may be formed by the same base material, or may be formed of a different base material, the point at which the cover is not provided with the organic EL element on the surface is different from that of the substrate.

The organic EL device includes a laminate of an anode/light emitting layer/negative electrode. A passivation film such as a SiN film may be provided as needed.

The method of forming the crucible by coating the composition for encapsulation of the present invention in a line on the cover is not particularly limited, and can be carried out, for example, using a dispenser or the like.

The height of the crucible or the thickness of the encapsulating layer is not particularly limited as long as it can achieve the purpose of protecting the element from water or the like.

The method of filling the filler in the crucible is not particularly limited and can be carried out using, for example, a dispenser.

According to the above method, since the substrate on which the organic EL element is disposed is bonded after light irradiation of the package layer provided on the cover, the organic EL element can be prevented from being directly exposed to UV, thereby preventing UV-induced Deterioration of the organic EL element. Moreover, the cured product of the package composition of the present invention has both low exhaustivity and moisture resistance, and the organic EL device of the present invention has an outer periphery of the organic EL element by the inclusion of the hardened material. In this configuration, it is possible to prevent deterioration of the organic EL element due to moisture or exhaust gas, and it is possible to maintain excellent light-emitting characteristics over a long period of time.

In the organic EL device obtained by the above method, since the organic EL device is not deteriorated by exposure to UV during packaging, and is protected by a cured product having both low exhaust and moisture resistance, it has a long life and is reliable. High sex.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the examples. In addition, the viscosity was measured at 25 ° C and a shear rate of 20 (1/s) measured by a rheometer (trade name "Physica MCR301", manufactured by Anton Paar Co., Ltd.).

Example 1

According to the places listed in the table (unit: parts by weight), each component is put into a self-rotating ‧ revolution mixer (trade name "Awatori Rentaro ARE-310" In the Thinky system, stirring was carried out to obtain a package composition (1).

The obtained package composition (1) was applied onto a glass substrate to form a coating film (1) (thickness: 100 μm), and ultraviolet rays were irradiated with a mercury lamp (irradiation amount: 1600 mJ/cm ² ). The viscosity before ultraviolet irradiation, immediately after irradiation of ultraviolet rays, and 30 minutes after ultraviolet irradiation was measured, and the degree of viscosity increase from the ultraviolet irradiation immediately after irradiation to 30 minutes after the ultraviolet irradiation was calculated by the following formula.

Viscosity rise = viscosity during 30 minutes after UV irradiation / viscosity after UV irradiation

Then, the coating film (1) after ultraviolet irradiation was heated at 100 ° C for 1 hour to obtain a cured product (1) (post cure).

Regarding the obtained cured product (1), the amount of exhaust gas and the water vapor permeability were evaluated by the following methods.

Examples 2 to 4 and Comparative Examples 1 to 3

A composition for encapsulation was obtained in the same manner as in Example 1 except that the prescription was changed, and a coating film was obtained to obtain a cured product.

Regarding the obtained cured product, the amount of exhaust gas and the water vapor permeability were evaluated by the following methods.

<discharge amount>

The amount of the hardened material from the hardening retarder (unit: ppm) was added to a vial to 60 mg of the cured product, subjected to UV irradiation (2000 mJ/cm ² ), and allowed to stand at 100 ° C for 1 hour. Determine the amount of exhaust in the vial. Further, a calibration curve was prepared using a toluene standard solution [toluene: 100 ppm as a standard substance, solvent: hexane (60 mg)]. In the measurement equipment, the product name "HP-6890N" (manufactured by Hewlett-Packard Co., Ltd.) was used, and the product name "DB-624" (manufactured by Agilent Co., Ltd.) was used for the column.

<moisture resistance>

The moisture resistance of the cured product is the moisture permeability (g/m ² ‧day‧atm) of the cured product (thickness: 100 μm), according to JIS L 1099 and JIS Z 0208 (cup method), at 60 ° C, 90% It was evaluated by measurement under RH conditions.

The compounds used in the examples and comparative examples are shown below.

(cationic curable compound)

(A)-1: (3,4,3',4'-diepoxy)bicyclohexane

(Photocationic polymerization initiator)

(B)-1: 4-(4-biphenylthio)phenyl-4-biphenylphenylhydrazine 肆(pentafluorophenyl)borate

(hardening retarder)

(C)-1:1,3,4,6-tetraglycidyl acetylene urea, trade name "TG-G , Shikoku Chemical Industry Co., Ltd.

(C)-2: 1,3,4,6-Telylpropylacetylene, trade name "TA-G", Shikoku Chemical Industry Co., Ltd.

(C)-3: N,N,N',N'-tetraglycidyl-1,3-benzenedi(methylamine), trade name "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.

(C)-4: Crown ether, trade name "18-crown-6", Japan Soda (share) system

(C)-5: bisphenol A bis(triethylene glycol glycidyl ether) ether, trade name "Rikaresin BEO-60E", New Japan Physical and Chemical Co., Ltd.

(C)-6:1,3,5-gin(4,5-epoxypentyl)-1,3,5-three -2,4,6-trione, trade name "TEPIC-VL", Nissan Chemical Industry Co., Ltd.

(inorganic filler)

(D)-1: talc, average particle size 1.5 μm, tabular particles, trade name "FG-15", NIPPON TALC (share) system

(D)-2: mica, average particle size 3.4 to 5.5 μm, tabular particles, trade name "MK-100", manufactured by Co-op Chemical Co., Ltd.

(Other cationic hardening compounds)

(E)-1: Liquid bisphenol F diglycidyl ether, trade name "YL-983U", manufactured by Mitsubishi Chemical Corporation

(E)-2: o-phenylphenol glycidyl ether, trade name "SY-OPG", manufactured by Sakamoto Pharmaceutical Co., Ltd.

[Industrial availability]

In the composition for organic EL device encapsulation of the present invention, even if UV is applied to the crucible formed on the lid, the curing can be suppressed until the heat treatment is performed, even with the substrate having the organic EL element. The post-cooperation industry has been delayed, and there has been no loss of connectivity, which has caused difficulties in fitting. After the bonding, heat treatment can be performed by performing heat treatment, and the organic EL element can be packaged without directly exposing it to UV. Moreover, the composition for organic EL element encapsulation of the present invention can form a cured product which is excellent in moisture resistance and low in venting property, and can prevent deterioration of the organic EL element due to exhaust gas.

Therefore, the composition for organic EL element encapsulation of the present invention can be suitably used as a material for packaging an organic EL element (particularly, a top emission type organic EL element) by a cofferdam filling method.

Claims (8)

A composition for encapsulating an organic electroluminescence device, which is a composition used as a coffin when encapsulating an organic electroluminescence device by a dam and fill method, and contains the following components (A) and components (B), component (C), and component (D): component (A): one or more selected from the group consisting of an alicyclic epoxy group, an oxetane ring, and an epoxy group in one molecule. a cationically curable compound based on an episulfide group and a vinyl ether group (excluding a compound corresponding to the component (C)); a component (B): a photocationic polymerization initiator; and a component (C): selected from the group consisting of At least one of an N-glycidyl compound, an N-vinyl compound, and an N-allyl compound (excluding N-glycidyl isocyanurate); Component (D): an inorganic filler. The composition for encapsulating an organic electroluminescence device according to claim 1, wherein the component (C) is a compound represented by the following formula (c-1): (In the formula (c-1), R ^a represents a single bond to form the via structure from a hydrocarbon, the heterocyclic ring structure of formula, or a hydrocarbon group with a heterocyclic structure of formula t removing hydrogen atoms; R ^b represents a group selected a hydrogen atom, or a hydrocarbon group, a heterocyclic group, and the group in a group bonded via a single bond; R ^c represents at least one selected from the group consisting of glycidyl group, vinyl group, and allyl group; s represents 1 or 2; t represents an integer of 1 or more; in the case where t is 2 or more, the bases in 2 or more square brackets may be the same or different), and/or the following formula (c-2) Compounds shown: (In the formula (c-2), the ring Z represents a hetero ring containing a nitrogen atom; R ^c represents at least one group selected from the group consisting of a glycidyl group, a vinyl group, and an allyl group; and u represents an integer of 1 or more; When u is 2 or more, two or more nitrogen atoms contained in the ring Z may be directly bonded or may be bonded via another atom. The composition for encapsulating an organic electroluminescence device according to claim 1 or 2, wherein the component (C) is contained in an amount of 0.05 to 3 parts by weight based on 1 part by weight of the component (B). The composition for encapsulating an organic electroluminescence device according to any one of claims 1 to 3, further comprising the following component (E): component (E): one or more glycidyl ether groups in one molecule Compound (excluding the compound corresponding to the component (A) and the component (C)). The composition for encapsulating an organic electroluminescence device according to any one of claims 1 to 4, wherein the component (D) is an inorganic filler having an average particle diameter of 0.001 to 30 μm. The composition for encapsulating an organic electroluminescence device according to any one of claims 1 to 5, wherein the component (D) is a flat inorganic filler. A method of manufacturing an organic electroluminescence device, comprising the step of encapsulating an organic electroluminescence device, the step comprising the following 1~3: 1: coating the composition for encapsulating the organic electroluminescent element according to any one of claims 1 to 6 on the lid to form a crucible; 2: applying light irradiation to the crucible; and 3: a lid having a crucible after irradiation with light, The substrate on which the organic electroluminescent element has been placed is bonded and heat-treated. An organic electroluminescence device having a configuration in which a crucible is disposed around a periphery of an organic electroluminescence device, the crucible comprising the composition for encapsulating an organic electroluminescence device according to any one of claims 1 to 6. Hardened material.