KR20160030080A - Organic el element - Google Patents

Abstract

Provided is a water entrapment body that can be handled under air, and an organic EL element having the water entrapment body is provided. The composition for forming a water entrapment body is formed by mixing at least one compound selected from the group consisting of a compound having a hydrolysable group and at least one compound selected from the group consisting of an acid generator and a base generator and a curing compound as a component Prepare. And the water entrapment body 30 is formed using the water entrapment body forming composition. The moisture trapping body 30 is sealed in the structure body 20 together with the organic EL layer 10 including the organic luminescent layer so as to be shielded from the outside air to provide the organic EL element 100. [

Description

[0002] Organic EL devices [0003]

The present invention relates to an organic EL device.

BACKGROUND ART [0002] Organic electronic luminescence (EL) devices are known as one of electronic devices that are being actively developed in recent years. The organic EL device is a simple device having a laminated structure composed of an anode / organic light emitting layer / cathode as a basic structure, but has a problem that the organic light emitting layer is susceptible to moisture.

That is, the organic EL element is concerned with the formation of a so-called dark spot due to the influences of moisture penetrated into the element along with the prolongation of the driving period, and there is a fear that the luminescence properties such as luminance and luminous efficiency are gradually lowered I have. Therefore, it is necessary to remove the moisture in the element and use it in a more closed state, but it is difficult to completely seal the electronic device by sealing.

Thus, an organic EL device has been proposed in which a moisture trapping agent made of a specific organometallic compound is disposed in advance in a device, and water is trapped in the moisture trapping agent to keep the inside of the device in a low humidity environment (see, for example, See Document 1).

Japanese Patent Publication No. 3936151

However, for example, the organoaluminum compound exemplified as the water trapping agent in Patent Document 1 and the like is highly reactive and may react with water in the air. Therefore, it is difficult to handle in the air, and in the case of using a conventional moisture capturing agent, handling under air or nitrogen controlled at a sufficiently low humidity is essential. In addition, in the case of manufacturing an organic EL device using a conventional moisture capturing agent, a work in a low-humidity atmosphere is required, and the manufacturing process is complicated.

Therefore, there is a demand for a moisture trapping member that can be handled under normal air and can be used in the production of electronic devices such as organic EL devices. There is also a demand for an organic EL device having a moisture trapping body capable of removing moisture in the device and reducing the intrusion of moisture into the device and handling the same under air.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an electronic device such as an organic EL device and a liquid crystal display device, which is capable of removing water in the device and reducing intrusion of moisture into the device and providing a moisture trapping body And an object of the present invention is to provide an organic EL device including the moisture trapping body.

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems. As a result, it has been found that the above problems can be solved by the organic EL device having the following constitution, and the present invention has been completed.

For example, the present invention relates to the following [1] to [5].

[1] An organic EL device having a moisture trapping body,

Wherein the water-

(A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound,

(B) at least one compound selected from the group consisting of an acid generator and a base generator,

(C) a curable compound.

[2] The process according to [1], wherein the compound (A)

(A1) at least one compound selected from a compound represented by the formula (A1-1), a compound represented by the formula (A1-2) and a compound represented by the formula (A1-3)

(A2) at least one compound selected from a carbonic anhydride and a carbonic acid compound, and

(A3) at least one compound selected from the group consisting of a compound represented by the formula (A3-1), a compound represented by the formula (A3-2) and a compound represented by the formula (A3-3) ≪ / RTI &

The organic EL device according to [1], wherein the compound (B) is an acid generator,

Wherein R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or a group having 1 to 18 carbon atoms R ³ , R ⁴ and R ⁷ may be combined with a carbon atom to which they are directly bonded to form a cyclic structure, n is 0 or an integer of 1 to 18, * represents a bonding position ;

In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms;

R ⁸ is each independently an organic group having 3 to 30 carbon atoms;

In the formula (A1-3), the formula R ⁸ is the same as the formula (A1-2);

[In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom;

R ²¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group;

R ²² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxirane group, a 3,4-epoxycyclohexyl group, or a mercapto group;

p is an integer from 0 to 6;

r is an integer of 0 to 2, and s is an integer of 1 to 30;

[3] The process according to [1], wherein the compound (A)

(A2) at least one compound selected from a carbonic anhydride and a carbonic acid compound, and

(A3) at least one compound selected from the group consisting of a compound represented by the formula (A3-1), a compound represented by the formula (A3-2) and a compound represented by the formula (A3-3) ≪ / RTI &

The organic EL device according to [1], wherein the compound (B) is a base generator:

[In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom;

R ²¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group;

R ²² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxirane group, a 3,4-epoxycyclohexyl group, or a mercapto group;

p is an integer from 0 to 6;

r is an integer of 0 to 2, and s is an integer of 1 to 30;

[4] The organic EL device according to any one of [1] to [3], wherein the moisture trapping body further comprises (D) a radical polymerization initiator.

[5] The organic EL device according to any one of [1] to [4], wherein the moisture trapping body further contains (E) fine particles.

According to the present invention, in an electronic device such as an organic EL device and a liquid crystal display device, it is possible to remove moisture in the device, reduce intrusion of moisture into the device, and use a moisture trapping body capable of handling under air, It is possible to provide an organic EL element such as an organic EL illuminator or an organic EL display element which can suppress occurrence of dark spots even when driven.

1 is a cross-sectional view schematically showing a first example of an organic EL device according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing a second example of the organic EL device according to the embodiment of the present invention.
3 is a cross-sectional view schematically showing a third example of the organic EL device according to the embodiment of the present invention.
4 is a cross-sectional view schematically showing a fourth example of the organic EL device according to the embodiment of the present invention.
5 is a cross-sectional view schematically showing a fifth example of the organic EL device according to the embodiment of the present invention.

(Mode for carrying out the invention)

The organic EL device of the present invention comprises the moisture trapping body of the present invention. The water entrapment body of the present invention is formed using the water entrapment body forming composition of the present invention.

Hereinafter, the composition for forming a water entrapment body of the present invention for forming the water entrapment body of the present invention will be described. The water entrapment body of the present invention formed using the composition for forming a water entrapment body and the present invention having the water entrapment body Will be described.

[Moisture trapping body forming composition]

The moisture entrapment forming composition of the present invention is characterized by comprising at least one compound selected from the group consisting of a compound having a hydrolysable group and at least one compound selected from the group consisting of an acid generator and a base generator and a curing compound .

Each component will be described in detail below.

In the following description, at least one kind of compound selected from the group consisting of a compound having a hydrolysable group and a hydrolyzate, an acid generator and a base generator, and a curing compound (A), the acid / base generator (B), and the curing compound (C), are also referred to as water trapping agent (A) Are also referred to as component (A), component (B) and component (C), respectively. The same is true for the other examples, unless otherwise specified.

[Moisture capturing agent (A)]

The water trapping agent (A) is, for example, a compound having a structure capable of hydrolyzing in the presence of an acid or a base, that is, a hydrolyzate. Examples of the water trapping agent (A) include at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), a carboxylic acid anhydride (A3) selected from a compound represented by formula (A2), a compound represented by formula (A3-1) and a compound represented by formula (A3-2). Each of these compounds (A1) to (A3) may be used alone or in combination of two or more. In the following description, the compounds (A1) to (A3) are also referred to as moisture trapping agents (A1) to (A3), respectively.

≪ Water entrapment agent (A1) >

The water trapping agent (A1) is at least one compound selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2). The water trapping agent (A1) is stable because of its low reactivity with water under neutral and alkaline conditions, but easily causes a hydrolysis reaction in the presence of an acid.

In the formula (A1-1), R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms;

R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms;

R ³ , R ⁴ and R ⁷ may be taken together with a carbon atom to which they are directly bonded to form a cyclic structure;

n is 0 or an integer from 1 to 18;

* Indicates the binding position. In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms;

R ⁸ is independently an organic group having 3 to 30 carbon atoms.

In the explanation of the formulas according to the water capturing agent (A1), unless otherwise specified,

Examples of the organic group having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, Straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably alkyl group having 1 to 6 carbon atoms, such as hexyl, decyl, dodecyl and octadecyl;

Cycloalkyl groups having 3 to 12 carbon atoms such as cyclohexyl and methylcyclohexyl;

Cycloalkyl substituted alkyl groups having 4 to 18 carbon atoms such as cyclohexylmethyl and cyclohexylethyl;

A phenyl group;

Aralkyl groups having 7 to 18 carbon atoms such as phenyl-substituted alkyl groups (e.g., benzyl group, phenethyl group);

A group in which a part of these groups is substituted with an oxygen atom (hereinafter also referred to as " oxygen atom substituent ");

Vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, glycidyl group;

A carboxyl group, and may be a group represented by the following formulas g1 to g7;

Examples of the "organic group having 3 to 30 carbon atoms" include an alkylene group, a hydroxyalkylene group, an alkyl group, a vinyl group, an allyl group, a (meth) acryloyloxy group, an oxiranyl group, an oxetanyl group, Quot ;, and organic groups having 3 to 20 carbon atoms and at least one group selected from groups represented by the following formulas g1 to g7. In the following formulas g1 to g7, * represents a bonding position.

Examples of the above-mentioned oxygen atom substituent include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl;

Alkanoyloxyalkyl groups such as acetoxymethyl and acetoxyethyl;

Aryloxyalkyl groups such as phenoxymethyl and phenoxyethyl;

An alkoxy group such as methoxy;

An aryloxy group such as phenoxy;

And a hydroxyalkyl group such as hydroxymethyl.

The total number of carbon atoms of the group represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formula (A1-1) (when n is 0, the number of carbon atoms of the group represented by R ² to R ⁵ Is preferably from 0 to 18, more preferably from 0 to 12, from the viewpoints of the absorption ability and the solubility.

In addition, R ³ , R ⁴ and R ⁷ (when n = 0, R ³ and R ⁴ ) in the formula (A1-1) are combined with the carbon atoms to which they are directly bonded to form a cyclic structure good. Examples of the cyclic structure include a cyclohexane ring and a cyclopentane ring.

In the formula (A1-1), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom.

In the formula (A1-1), R ² to R ⁵ each independently represent a hydrogen atom, the alkyl group having 1 to 18 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, the cycloalkyl substituted alkyl group having 4 to 18 carbon atoms, A phenyl group, an aralkyl group having 7 to 18 carbon atoms, and an oxygen atom substituent, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.

In the formula (A1-1), R ⁶ to R ⁷ each independently represent a hydrogen atom, a hydroxyl group, the alkyl group having 1 to 18 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, the cycloalkyl group having 4 to 18 carbon atoms An alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, an oxygen atom substituent, a vinyl group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, glycidyl group, , More preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the above formulas g1 to g2.

R ¹ to R ⁷ in the formula (A1-1) are preferably the above-mentioned atom or group from the viewpoint of the absorption ability of the water capturing agent (A) and compatibility with other components.

In the formula (A1-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R ⁶ and R ⁷ may be the same or different.

In the formula (A1-2), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁸ is preferably independently a group represented by the formulas g1 to g7.

[Compound having structure moiety represented by formula (A1-1)] [

The compound having a structural moiety represented by the formula (A1-1) includes, for example, a compound represented by the following formula. More specifically, as described later, there can be mentioned a compound obtained by reacting an orthoester (a1), a polyhydric alcohol (a2) and a hydroxyl group-containing compound (a3), and specific examples thereof include a compound represented by the formula (A1- , The formula (A1-ii) and the formula (A1-iii).

Wherein A is a structural moiety represented by formula (A1-1);

Y is a residue obtained by removing m (2? M? P) hydroxyl groups from a hydroxyl group-containing compound (a3) described below and having p (p? 2) hydroxyl groups in one molecule;

m is an integer of 2 to p.

Examples of the compound having a structural moiety represented by the formula (A1-1) include a compound obtained by reacting an orthoester (a1), a polyhydric alcohol (a2) and a hydroxyl group-containing compound (a3) described below .

(Orthoester (a1))

The orthoester (a1) is a compound represented by the following formula (a1).

In formula (a1), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms;

Each of the three Rx's is independently an organic group having 1 to 18 carbon atoms. The organic group is preferably the straight chain or branched chain alkyl group having 1 to 18 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, or the cycloalkyl substituted alkyl group having 4 to 18 carbon atoms, and the straight or branched chain More preferably an alkyl group having 1 to 6 carbon atoms.

Examples of the orthoester (a1) include methyl orthoformate, ethyl orthoformate, orthoformate butyl, orthoformate methyl, orthoacetate, methyl orthoacetate, ethyl ortho propionate, methyl ortho butyrate, ethyl ortho butyrate . Among these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate and ethyl orthoacetate are preferable.

The orthoester (a1) may be used singly or in combination of two or more.

(Polyhydric alcohol (a2))

As the polyhydric alcohol (a2), for example, a compound having two or more hydroxyl groups in one molecule can be mentioned, and a compound represented by the formula (a2-1) is preferable. Specifically, there may be mentioned? -Glycol having two hydroxyl groups in one molecule, and compounds having two or more hydroxyl groups in one molecule other than? -Glycol.

In the formula (a2-1), R ² to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms. R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or an organic group having 1 to 18 carbon atoms. R ³ , R ⁴ and R ⁷ may be taken together with a carbon atom to which they are directly bonded to form a cyclic structure. R ² to R ⁷ in the formula (a2-1) have the same meanings as the symbols in the formula (A1-1), and the preferred examples are also the same as the description in the formula (A1-1).

In the formula (a2-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, more preferably 1. When n is an integer of 2 or more, R ⁶ and R ⁷ may be the same or different.

An? -glycol in which n is 0 is preferable. The? -glycol has two adjacent hydroxyl groups. Accordingly, the reaction between the orthoester and the? -Glycol proceeds efficiently and is suitable for the production of the water trap agent.

Examples of the? -glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, pinacol, hydrolyzate of long chain alkyl monoepoxide;

Fatty acid monoglycerides (? Form) such as glycerin monoacetate (? Form) and glycerin monostearate (? Form);

3-ethoxypropane-1,2-diol, and 3-phenoxypropane-1,2-diol. Of these, ethylene glycol, 1,2-propylene glycol and 1,2-hexanediol are preferred.

Particularly preferred are compounds wherein n is 1. The compound has two or three or more hydroxyl groups in the same proximity to the aforementioned? -Glycol. Accordingly, the reaction between the orthoester and the above compound proceeds efficiently and is suitable for the synthesis of the orthoester compound (A1-1).

Examples of the compound wherein n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,3-pentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, Diol, (2-aryloxymethyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2- ethylpropane-1,3-diol, glycerin, 1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylol propionic acid, dimethylolbutanoic acid, 2-ethyl- Octanediol, 1,3-dihydroxycyclohexane;

Glycerin monoacetate (? -Form), glycerin monostearate (? -Form), and other fatty acid monoglycerides (? -Form). Among these, preferred are neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl- ) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol and glycerin.

(Hydroxyl group-containing compound (a3))

The hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule.

When the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, the hydroxyl group-containing compound (a3) is selected from among the polyhydric alcohol (a2) . In this case, as the compound selected as the hydroxyl group-containing compound (a3), a compound other than the compound selected as the polyhydric alcohol (a2) is preferably selected.

Examples of the hydroxyl group-containing compound (a3) include a compound having two hydroxyl groups in one molecule and a compound having three or more, preferably three to four, hydroxyl groups in one molecule.

Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5- Methyl-1,5-pentanediol, 1,4-dimethylol cyclohexane, tricyclodecanedimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate Bisphenol A, bisphenol F, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3 Tetraoxaspiro [5,5] undecane, diethylene glycol, triethylene glycol, polyethylene glycol higher than tetra, Dipropylene glycol, tripropylene glycol, tetraester or higher polypropylene glycol, and copolymers of ethylene oxide and propylene oxide and having hydroxyl groups at both terminals A linear polyester having a hydroxyl group at both ends such as a polycaprolactone diol, a polycarbonate diol, and a carbonic acid adduct of a diepoxide.

Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (Polyether, acrylic polymer, ketone resin, phenol resin, epoxy resin, urethane resin, polyether polyol, polyether polyol, polyether polyol, And natural saccharides such as polyvinyl alcohol and glucose which are saponified polyvinyl acetate).

As the hydroxyl group-containing compound (a3), a compound having a molecular weight in the range of 90 to 100,000, particularly 90 to 5000, is preferable. As the hydroxyl group-containing compound (a3), a compound having a hydroxyl value in the range of 20 mgKOH / g to 1850 mgKOH / g, particularly 40 mgKOH / g to 1650 mgKOH / g is preferable.

(Reaction rate)

(A1) and the polyhydric alcohol (a2) in the production of the orthoester compound (A1-1) by reacting the above-mentioned orthoester (a1), polyhydric alcohol (a2) and hydroxyl group- And the hydroxyl group-containing compound (a3) is not particularly limited.

For example, the amount of the orthoester (a1) is 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol, per mol of the hydroxyl group in the hydroxyl group-containing compound (a3) And the amount of the polyhydric alcohol (a2) is in the range of 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, and more preferably 0.1 mol to 2 mol, And the like. When the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2), the compound selected as the hydroxyl group-containing compound (a3) other than the compound selected as the polyhydric alcohol (a2) is selected.

The water trapping agent (A1) can be obtained by condensation reaction of three components of the orthoester (a1), the polyhydric alcohol (a2) and the hydroxyl group-containing compound (a3). For example, the above-mentioned three components may be reacted in the presence of an acid catalyst such as an organic solvent and formic acid at a temperature usually in the range of room temperature to 250 캜, preferably 70 캜 to 200 캜 for 1 hour to 20 For about one hour, and condensation reaction can be appropriately carried out. The group of the compound obtained by the above method may be converted into another group by a known method. As for the synthesis method, for example, International Publication WO01 / 01611 can be referred to.

In this way, a water trapping agent (A1) having a structure in which the hydroxyl group in the hydroxyl group-containing compound (a3) is blocked by a 5-membered ring or a 6-membered ring formed of the orthoester (a1) and the polyhydric alcohol (a2) can be obtained.

(Example of a compound having a structural moiety represented by the formula (A1-1)) [

Specific examples of the compound having a structural moiety represented by formula (A1-1) include compounds represented by formula (A1-i), formula (A1-ii) and formula (A1-iii).

Y ¹ in the formula (A1-i) is an m-valent residue obtained by removing m (2? M? P) hydroxyl groups from a compound having p (p = 2-6) hydroxyl groups in one molecule. R ¹ to R ⁷ and n are the same as R ¹ to R ⁷ and n in the formula (A1-1). The compound represented by the formula (A1-i) can be obtained by, for example, an orthoester of the formula (a1), a polyhydric alcohol of the formula (a2-1) and a hydroxyl group having 2 to 6 hydroxyl groups Containing compound (a3) as a raw material.

In the formulas (A1-ⅱ), Y ² is a hydroxyl group that two to remove divalent residue from a compound having two hydroxyl groups in one molecule. R ¹ to R ⁷ and n are the same as R ¹ to R ⁷ and n in formula (A1-1). The compound can be synthesized by using, for example, an orthoester of the formula (a1), a polyhydric alcohol of the formula (a2-1) and a hydroxyl group-containing compound (a3) having two hydroxyl groups in one molecule as raw materials have.

In the formulas (A1-ⅲ), Y ³ is a residue tetravalent removal of the four hydroxyl groups from a compound having four hydroxyl groups in a molecule. R ¹ to R ⁷ and n are the same as R ¹ to R ⁷ and n in the formula (A1-1). The compound can be obtained by, for example, using the orthoester of the formula (a1), the polyhydric alcohol of the formula (a2-1) and the hydroxyl group-containing compound (a3) , Can be synthesized.

[Compound represented by formula (A1-2)] [

As a specific example of the compound having a structural moiety represented by the formula (A1-2), for example, a compound represented by the following formula can be given.

≪ Water capturing agent (A2) >

The water trapping agent (A2) is a carbonic acid anhydride, and examples thereof include an anhydride of a monocarboxylic acid, a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride. The water-trapping agent (A2) is stable because of its low reactivity with water under neutral conditions, but readily undergoes a hydrolysis reaction in the presence of an acid or a base.

[Anhydrous monocarboxylic acid]

Examples of the anhydrides of monocarboxylic acids include trifluoroacetic anhydride, benzoic anhydride, isostornic anhydride, isopentanoic anhydride, isobutyric anhydride, n-valeric anhydride and crotonic anhydride. The carbon number of the anhydride of the monocarbonic acid is preferably 4 to 20, more preferably 4 to 14, from the viewpoint of the volatility of the carbonic acid which can be produced by hydrolysis.

[Dicarboxylic anhydride]

As the dicarboxylic anhydride, a compound represented by the following formula (A2-1) can be mentioned.

In the formula (A2-1), Ra represents a divalent organic group such as an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an aromatic group directly or via a bridging group (e.g., A non-condensed polycyclic aromatic group linked to each other by -O-, -CO-, -S-, -SO ₂ -, an alkylene group, -C (CF ₃ ) ₂ - The carbon number of Ra is usually 1 to 30, but is preferably 4 to 30, and more preferably 6 to 18 from the viewpoint of the volatility of the dicarboxylic acid which can be produced by hydrolysis.

Examples of the aforementioned dicarboxylic anhydrides include aliphatic dicarboxylic anhydrides, alicyclic dicarboxylic anhydrides, and aromatic dicarboxylic anhydrides.

Examples of the above-mentioned aliphatic dicarboxylic anhydrides include anhydrides of aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid;

And anhydrides of aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, mesaconic acid and citraconic acid.

Examples of the above-mentioned alicyclic dicarboxylic anhydrides include anhydrides of alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, hexahydroterephthalic acid and 4-methylcyclohexanedicarboxylic anhydride.

The above-mentioned aromatic dicarboxylic anhydride means a dicarboxylic anhydride of an organic compound in which at least two carboxyl groups are bonded to an aromatic ring. Examples of the aromatic dicarboxylic anhydride include phthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, 2,3-dicarboxyphenylphenyl ether, 3,4-dicarboxyphenylphenyl ether, 2,3-dicarboxyphenylphenylsulfone, 2,3-dicarboxyphenylphenylsulfide, 3, 4-biphenyldicarboxylic acid, 2,3- , 4-dicarboxyphenylphenylsulfide, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,2-anthracenedicarboxylic acid, 2,3- And anhydrides of aromatic dicarboxylic acids such as 1,9-anthracenedicarboxylic acid.

The dicarboxylic anhydride, which is the water capturing agent (A2), may be used singly or in combination of two or more.

[Tetracarboxylic acid dianhydride]

As the tetracarboxylic acid dianhydride, a compound represented by the following formula (A2-2) can be mentioned.

In the formula (A2-2), Rb represents a tetravalent organic group such as an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an aromatic group, A non-condensed polycyclic aromatic group linked to each other by -O-, -CO-, -S-, -SO ₂ -, an alkylene group, -C (CF ₃ ) ₂ - The carbon number of Rb is usually 4 to 100, but is preferably 4 to 30, and more preferably 4 to 18 in terms of the volatility of the tetracarboxylic acid that can be produced by hydrolysis.

Examples of the aforementioned tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride.

Examples of the aforementioned aliphatic and alicyclic tetracarboxylic acid dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2, Cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1 , 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3, 5,6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] , 9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ , 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro- c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro- [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro- -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5- dioxotetrahydrofuranyl) -3-methyl- - Dicarboxylic dianhydride, bicycle (T-1) and (T-2), respectively. The compounds represented by the formulas have.

In the formulas (T-1) and (T-2), R ¹¹ and R ¹³ are divalent organic groups having an aromatic ring;

R ¹² and R ¹⁴ are each a hydrogen atom or an alkyl group, and plural R ¹² and R ¹⁴ present may be the same or different.

An aromatic tetracarboxylic acid dianhydride refers to a tetracarboxylic anhydride of an organic compound in which at least four carboxyl groups are bonded to an aromatic ring. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetra Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarbon 3,3 ', 4,4'-diphenylmethane tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'- 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4 , 4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (tree Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) Bis (anhydrotrimellitate), 1,6-hexane (anhydrous trimellitate), diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol- Bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- 2,3,4,5-pyridine tetracarboxylic acid dianhydride, 2,6-bis (3,4-dicarboxyphenyl) pyridine, and (T-3-1) to . ≪ / RTI >

The tetracarboxylic acid dianhydride as the water trapping agent (A2) may be used singly or in combination of two or more kinds.

≪ Water entrapment agent (A3) >

The water entrapping agent (A3) is at least one selected from a compound represented by the formula (A3-1) and a compound represented by the formula (A3-2). The water trapping agent (A3) is stable because of its low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.

In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom, or a zirconium atom. Among them, a silicon atom is preferable.

In the formula (A3-1) and (A3-2), R ²¹ is a (meth) acryloyl group, oxiranyl group, oxetanyl group, 3,4-epoxy cyclohexyl group, mercapto group and an isocyanate group from earthenware An organic group having at least one selected group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group.

The formula (A3-1) and (A3-2) of, R ²² is a hydrogen atom, a substituent having a carbon number of alkyl group of 1 to 20 is also good, a cycloalkyl group of 3 to 12 carbon atoms which may have a substituent, a substituent (Meth) acryloyloxy group, a glycidoxy group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, or a mercapto group.

Among the formulas (A3-1) and (A3-2), r is an integer of 0 to 2;

p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3. s is an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

- (CH ₂ ) _p -R ²² may be the same or different. When there are a plurality of groups represented by -OR ²¹ , they may be the same or different.

Examples of the organic group represented by R ²¹ in the formulas (A3-1) and (A3-2) include groups represented by the following formulas. Wherein R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents an alkylene group having 1 to 3 carbon atoms, and n represents an integer of 1 to 3.

The alkyl group in R ²¹ in the formulas (A3-1) and (A3-2) may be either linear or branched, and includes, for example, methyl, ethyl, Propyl, n-butyl, isobutyl, t-butyl, pentyl and hexyl. Examples of the cycloalkyl group include cyclohexyl.

In the compound represented by the formula and a compound the formula (A3-2) represented by (A3-1) of the component (A), the alkyl group may be any of straight chain, branched and cyclic would in R ^22. The alkyl group of R ²² has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples include, in addition to the alkyl group exemplified for R ²¹ , an n-pentyl group, an n-hexyl group, a n-hexyl group, n-heptadecyl group, n-tridecyl group, n-tridecyl group, n-tridecyl group, n-tridecyl group,

Examples of the aromatic hydrocarbon group in R ²² in the formulas (A3-1) and (A3-2) include a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, A tolyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among them, a phenyl group, a tolyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

The alkyl group, cycloalkyl group and aromatic hydrocarbon group in R ²² in the formulas (A3-1) and (A3-2) may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a nitro group A cyano group, and an alkoxy group having 1 to 6 carbon atoms. The position and the number of the substituent are arbitrary, and when two or more substituents are present, the substituents may be the same or different. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, and among them, a fluorine atom is preferable. The halogen atom may substitute a part or all of the hydrogen atoms of the alkyl group, the cycloalkyl group and the aromatic hydrocarbon group, but all of them are preferably substituted. Specific examples of the halogen-substituted alkyl group and the halogen-substituted cycloalkyl group include a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group and a perfluorocyclopropyl group, And a rosewax cycloalkyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group and an iso-propoxy group.

The (meth) acryloyloxy group in the aforementioned R ²² is a concept including an acryloyloxy group and a methacryloyloxy group.

Of the groups exemplified above, R ²² is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth) acryloyloxy group or a glycidoxy group. When a plurality of R < ²² > exist in the same molecule, they may be the same or different.

More specific examples of the compound represented by the formula (A3-1) and the compound represented by the formula (A3-2) which are the water entrapping agent (A3) include a silane compound wherein X is a silicon atom.

Examples of the silane compound wherein r is 0 and s is 1 in the compound represented by the above formula (A3-1) include two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane An alkoxysilane compound having

An alkoxysilane compound having two aromatic hydrocarbon groups having 6 to 14 carbon atoms such as diphenyldimethoxysilane;

Methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane (Meth) acryloyloxy group such as 3-acryloyloxypropylethyldimethoxysilane and 3-acryloyloxypropylmethyldiethoxysilane, and an alkoxysilane compound having an alkyl group having 1 to 20 carbon atoms;

3-methacryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldimethoxysilane, An alkoxysilane compound having a (meth) acryloyloxy group and an aromatic hydrocarbon group having 6 to 14 carbon atoms;

Alkoxysilane compounds having two (meth) acryloyloxy groups such as 3,3'-dimethacryloyloxypropyldimethoxysilane and 3,3'-diacryloyloxypropyldimethoxysilane;

Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysilane, and the like, An alkoxysilane compound having an alkyl group of 1 to 20;

3-glycidoxypropyldimethoxysilane, 3-glycidoxypropyldiethoxysilane, etc., and an alkoxysilane compound having an aromatic hydrocarbon group having 6 to 14 carbon atoms.

Examples of the silane compound wherein r is 1 and s is 1 in the compound represented by the formula (A3-1) include methyltrimethoxysilane, methyltriethoxysilane, methyltriiso- propoxysilane, 1 to 20 carbon atoms such as methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane and decyltrimethoxysilane. An alkoxysilane compound having one alkyl group;

An alkoxysilane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane;

An alkoxysilane compound having one aromatic hydrocarbon group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane;

Methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane Acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltripropoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.

Examples of the silane compound wherein r is 2 and s is 1 in the compound represented by the formula (A3-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso - propoxysilane, tetrabutoxysilane, tetraphenoxysilane and tetrabenzyloxysilane.

Examples of the compound represented by the above formula (A3-1) include compounds represented by the following formulas (A3-i), (A3-ii) and (A3-ii-2). The compound of the formula (A3-i), the formula (A3-ii) and the formula (A3-ii-2) can be produced by reacting a tetraethoxysilane with a hydroxyl group and a polymerizable group (oxiranyl, Oxetanyl group, (meth) acryloyl group, etc.) in the presence of an alkali.

Examples of the compound represented by the above formula (A3-1) include compounds represented by the following formulas (A3-iii) and (A3-iv). The compound represented by the formula (A3-iii) and the formula (A3-iv) can be produced by reacting a silane compound having a methoxy group with a hydroxyl group and a polymerizable group (oxiranyl, oxetanyl, And the like) in the presence of an alkali.

Examples of the compound represented by the above formula (A3-1) include compounds represented by the following formula (A3-v).

As the compound represented by the formula (A3-2)

Methacryloyloxypropyldimethylethoxysilane, 3-methacryloyloxypropyldimethylmethoxy silane, 3-methacryloyloxypropyldimethylethoxy silane, 3-methacryloyloxypropyldimethyl methoxy silane, 3- (Meth) acryloyloxy groups such as silane, 3-acryloyloxypropyldiethylmethoxysilane and 3-acryloyloxypropyldimethylethoxysilane, and having one alkyl group having 1 to 20 carbon atoms Alkoxysilane compounds;

Acryloyloxypropyldiphenylmethoxysilane, 3-acryloyloxypropyldiphenylsilane, 3-methacryloyloxypropyldiphenylmethoxysilane, 3-methacryloyloxypropyldiphenylethoxysilane, 3-acryloyloxypropyldiphenylmethoxysilane, 3- An alkoxysilane compound having one (meth) acryloyloxy group such as ethoxysilane and two aromatic hydrocarbon groups having 6 to 14 carbon atoms;

3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and the like, An alkoxysilane compound having two carbon atoms;

3-glycidoxypropyldiphenylmethoxysilane, and 3-glycidoxypropyldiphenylethoxysilane. Examples of the silane compound include a silane compound having two aromatic hydrocarbon groups each having 6 to 14 carbon atoms .

Examples of the compound represented by the formula (A3-1) and the compound represented by the formula (A3-2) which are the water trapping agent (A3) include those commercially available as commercial products such as OXT-191 ) And X-22-3000T (manufactured by Shin-Etsu Chemical Co., Ltd.).

≪ Explanation of action and effect &

The function and effect of the moisture trapping body forming composition of the embodiment of the present invention will be described below.

The composition for forming a water entrapment body of the embodiment of the present invention contains an acid / base generator (B), and if it receives at least one of heating and light irradiation, an acid or base is formed from the acid / base generator (B) . The acid or base accelerates the hydrolysis reaction of the water capturing agent (A) based on the water present in the system in which the water entrapment forming composition of the present embodiment is used, whereby water present in the system is consumed with high efficiency can do. In this specification, " capture of moisture " is used in this meaning. The hydrolysis product of the water entrapping agent (A) is less likely to deteriorate the performance of an electronic device such as an organic EL device and a liquid crystal display device as described later.

Therefore, in the present invention, when the water entrapment body of the organic EL device is formed by using the moisture trapping substance-forming composition, moisture in the device can be removed with high efficiency. In addition, it is considered that the moisture trapping agent (A) or the structural part derived therefrom remains in the water trapping material such as the encapsulating material formed of the moisture trapping forming composition of the embodiment of the present invention without decomposing. Therefore, it is possible to absorb moisture in the device for a long period of time even after the formation thereof, and deterioration of the characteristics of the organic EL device due to moisture can be suppressed.

Generally, the decomposition product is dispersed in the organic EL device by, for example, volatilizing, etc., and reaches the organic EL layer which becomes the light emitting layer of the organic EL device, and is contaminated to generate a dark spot. Which may deteriorate performance. However, in the present invention, since the hydrolysis product produced from the water capturing agent (A) has an appropriate molecular weight, volatilization or the like is suppressed, and the hydrolysis product can remain in the water entrapment such as an encapsulating material. The larger the molecular size of the hydrolysis product, the more easily the water trapping agent (A) remains in the water entrapment body, and therefore, a compound having a relatively large molecular weight is preferable.

The water trapping agent (A) used in the embodiment of the present invention hardly causes a highly volatile hydrolysis product such as a low molecular alcohol or the like even in the state of capturing moisture. For example, It is possible to suppress generation of dark spots due to adhesion of the decomposition products to the organic EL layer.

Examples of the hydrolysis reaction of the water trapping agent (A) (water trapping agents (A1) to (A3)) are shown below.

For example, regarding the hydrolysis reaction of the water capturing agent having the structure moiety of the formula (i-1) and the structure moiety of the formula (i-2), which is an example of the water entrapping agent (A1) The following chemical reaction formula can be shown. In the following formula, * represents a bonding position. It is considered that an alcohol compound is produced as a hydrolysis product. These alcohol compounds are hardly volatilized and have an appropriate molecular weight.

Examples of the water trapping agent (A2) include a monocarboxylic acid anhydride of the following formula (II-1), a dicarboxylic acid anhydride of the following formula (II-2) and a tetracarboxylic acid 2 of the following formula For the hydrolysis reaction of an anhydride, the following chemical reaction formula can be shown. It is considered that carbonic acid compounds such as carbonic acid (ii-1-1), dicarboxylic acid (ii-2-1) and tetracarboxylic acid (ii-3-1) are produced as the hydrolysis product. These carbonic acid compounds are hardly volatilized and have an appropriate molecular weight.

For example, the following chemical reaction formula can be shown for the hydrolysis reaction of the compounds of the formulas (iii-1) and (iii-2) which are examples of the water entrapping agent (A3). (Iii-1-1), metal hydroxides (iii-1-2), alcohol compounds (iii-2-1) and metal hydroxides (iii-2-2) as hydrolysis products. Unreacted R < ¹ > O in the metal hydroxide (iii-1-2) reacts with water to further generate an alcohol compound (iii-1-1). The alcohol compounds (iii-1-1) and (iii-2-1) may react in the R ²¹ group and remain in the water entrapped body. The metal hydroxides (iii-1-2) and (iii-2-2) may react in the R ²² group and stay in the water entrapped body. Further, the metal hydroxides (iii-1-2) and (iii-2-2) are fixedly held (held) in the water entrapped body by the R ²² group and scattered in the water entrapped body, The recurrence is prevented.

≪ Acid base generator (B) >

The composition for forming a water entrapment body of the embodiment of the present invention comprises at least one compound (B) (acid / base generator (B)) selected from the group consisting of an acid generator and a base generator . Hereinafter, the acid generator and the base generator which are components (B) of the water entrapment forming composition of the present embodiment are also referred to as "acid generator (B1)" and "base generator (B2)", respectively.

When the water entrapment forming composition of the embodiment of the present invention contains the acid generator (B1), at least one species selected from the water entraining agents (A1) to (A3) is used as the water entrapping agent (A). When the moisture trapping material-forming composition of the embodiment of the present invention contains the base generator (B2), at least one species selected from the water trapping agents (A2) to (A3) is used as the water trapping agent (A).

Examples of the acid generator (B1) include a radiation-sensitive acid generator and a thermal acid generator, and a radiation-sensitive acid generator is preferred. Examples of the base generator (B2) include a radiation-sensitive base generator and a thermal base generator, and a radiation-sensitive base generator is preferred.

The radiation-sensitive acid generators and the radiation-sensitive base generators can be defined as compounds capable of releasing an acidic active compound and a basic active compound, respectively, by irradiating them with radiation. The acidic active substance to be released serves as a catalyst for hydrolysis reaction of, for example, the aforementioned water capturing agent (A). The released alkaline active material functions as a catalyst for hydrolysis reaction of, for example, the water trapping agent (A2) and the water trapping agent (A3) described above.

Examples of the radiation to be irradiated for decomposing the radiation-sensitive acid generator or the radiation-sensitive base generator to generate the anion of the cationic or basic active material of the acidic active material include visible rays, ultraviolet rays, far ultraviolet rays, X And a charged particle beam. Among these radiation sources, ultraviolet rays are preferably used because they have a constant energy level, can attain a large curing rate, and are relatively inexpensive and compact.

In the composition for forming a water entrapment body of the embodiment of the present invention, the content of the component (B) in the case of the acid generator (B1) is preferably 0.001 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A) Mass part, and more preferably 0.01 mass part to 10 mass parts. When the content of the component (B) is within the above range, for example, a composition for forming a water entrapment body excellent in radiation sensitivity can be obtained.

In the composition for forming a water entrapment body of the embodiment of the present invention, the content of the component (B) in the case of the base generator (B2) is preferably 0.001 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A) Mass part, and more preferably 0.01 mass part to 10 mass parts. When the content of the component (B) is within the above range, for example, a composition for forming a water entrapment body excellent in radiation sensitivity can be obtained.

In the composition for forming a water entrapment body of the embodiment of the present invention, each of the acid generator (B1) and the base generator (B2) may be used alone or in combination of two or more.

[Acid generator (B1)]

As the acid generator (B1), for example, an anion curing catalyst such as an optical or thermal cationic curing catalyst such as an iodonium salt, a sulfonium salt or a phosphonium salt, an imidazole or an acid anhydride can be used. Of these, a cationic curing catalyst is preferred, and a cationic cation curing catalyst is more preferred. This is because the curing rate is high and the polymerization reaction is not initiated unless the light is shined, so that the storage stability is good.

Specific examples of the cationic curing catalyst include cations such as iodonium, sulfonium, and phosphonium substituted with an alkyl group or an aryl group, and cations such as SbF ₆ -, BF ₄ -, B (C ₆ F ₅ ) ₄ -, PF ₆ -, P (Rf) _n F _(6-n) - (Rf is, for example, a perfluoroalkyl group having 1 to 8 carbon atoms;

n is an integer of _{1~3), C n F 2n +1} SO 3 - (n is, for example, an integer of _{1~8), N (SO 2 CF} 3) 2 -, C (SO 2 CF 3) 3 - < / RTI > Specific examples of the surfactants include CPI-100P, CPI-101A, CPI-200K, CPI-210S and the like (manufactured by San Ai PRO) (Manufactured by Sanxin Chemical Industry Co., Ltd.), PI-2074 manufactured by Rhodia, Nippon Soda (registered trademark) SI-100L, (OPTON) CP series such as OPTIMER (registered trademark) SP series such as OPTIMER (registered trademark) SP-150, CP-66 and the like manufactured by Wako Junya Co., Series and WPI series.

Of these acid generators (B1), in cationic curing catalysts, anionic as B in terms of reactivity _{(C 6 F 5) 4 -} , P (Rf) n F (6-n) -, N (SO 2 CF 3 ) ₂ -, and C (SO ₂ CF ₃ ) ₃ - are preferable. As the cation, a sulfonium cation substituted with an alkyl group or an aryl group in view of storage stability is preferable.

[Base generator (B2)]

As the base generator (B2), a radiation-sensitive base generator is preferable, and the radiation-sensitive base generator is not particularly limited as long as it is a compound which generates a base such as amine by irradiation with radiation. Examples of the radiation-sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, acyloxyiminos, and?,? -Dimethyl-3,5-dimethoxybenzylcarbamates have.

Examples of the transition metal complexes include transition metal complexes such as bromopentaham ammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexammonium cobalt perchlorate, hexamethylamine cobalt perchlorate, Amine cobalt perchlorate.

Examples of the orthonitrobenzylcarbamates include, for example, [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[ Benzyl) oxy] carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2- nitrobenzyl) oxy] carbonyl] aniline, [(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [ [(2-nitrobenzyl) oxy] carbonyl] piperazine, [(2-nitrobenzyl) oxy] carbonyl] diaminobenzyl) oxy] carbonyl] toluenediamine, bis [ [(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] propylamine, Carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[ [(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-methylpropyl) (2,6-dinitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [ Carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine and 2-nitrophenylmethyl-4-methacryloyloxypyridine- .

Examples of the acyloxyimines include propionyl acetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyryl acetophenone oxime, butyrylbenzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, Adipoyl benzophenone oxime, adipoyl acetone oxime, acroyl acetophenone oxime, acroyl benzophenone oxime, and acroyl acetone oxime.

As other examples of the radiation-sensitive base generators, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, 2-nitrophenylmethyl-4-methacryloyloxypyridine- And acroleylbenzophenone oxime are particularly preferred.

≪ Curable compound (C) >

The moisture trapping body forming composition of the embodiment of the present invention contains the curing compound (C) as the component (C). The water entrapment body forming composition of the embodiment of the present invention can increase the crosslinking reactivity by containing the curable compound (C). The strength of the water entrapment body of the embodiment of the present invention formed of this moisture entrapment body forming composition and the adhesion with the substrate can be improved.

The curable compound (C) is a compound having a polymerizable group.

The curable compounds (C) may be used alone or in combination of two or more.

Examples of the curable compound (C) include a compound having a cyclic ether group and a compound having a polymerizable double bond.

Examples of the above-mentioned compound having a cyclic ether group include a compound having an epoxy group and a compound having an oxetanyl group.

As the above-mentioned compound having an epoxy group, for example,

As the monofunctional epoxy compound,

Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethyleneglycol glycidyl ether, phenol polyethylene glycol glycidyl ether , Phenylglycidyl ether, p-methylphenyl glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert- butylphenylglycidyl Etc,

As the polyfunctional epoxy compound,

Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglyme Polyglycidyl ethers of bisphenols such as cidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as cidyl ether;

Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene (1, 3-cyclohexanecarboxylic acid), ethylene- Epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexanecarboxylate), and lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate. .

As the above-mentioned oxetanyl group-containing compound, for example,

As the monofunctional oxetane compound,

Ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3- Ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, and the like,

As polyfunctional oxetane compounds,

Ethyl 3 - {[(3-ethyloxetane-3-yl) methoxymethyl] butane, Yl) methoxy] methyl} oxetane, and 1,1,1-tris [(3-ethyloxetan-3-yl) methoxymethyl] propane.

Among the above-mentioned compounds having a cyclic ether group, from the viewpoint of enhancing the crosslinking reactivity, compounds having an epoxy group are preferable, polyfunctional epoxy compounds are more preferable, polyglycidyl ethers of polyhydric alcohols are more preferable, Polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are particularly preferable.

As the above-mentioned compound having a polymerizable double bond, a compound having an oxygen atom is preferable, and a (meth) acrylate compound is more preferable.

Examples of the (meth) acrylate compound include monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds.

Examples of the monofunctional (meth) acrylate compound include (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyloxyethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, 2- 2-Hydro (Meth) acrylate, propyleneglycol mono (meth) acrylate, propyleneglycol mono (meth) acrylate, butoxyethyl (meth) (Meth) acrylate, isobornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy- 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (Meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2-bromophenoxyethyl (meth) acrylate, 4-bromo (Meth) acrylate, 2,4-dibromo (Meth) acrylate, 2,6-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6- (Meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (Meth) acrylate, tricyclohexane dimethanol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris Caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethyl (meth) acrylate, (Meth) acrylate, tripropylene glycol di (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol (Meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (metha) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa Acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethoxylated bisphenol A di (Meth) acrylate of phenol novolac polyglycidyl ether, 1,3-bis ((meth) acryloyloxy) -2-propanol, 9,9-bis [4- [2- Ethoxy] phenyl] -9H-fluorene, and the like. As the polyfunctional (meth) acrylate compound, polypropylene glycol di (meth) acrylate is preferable.

Examples of commercially available products of the aforementioned polyfunctional (meth) acrylate compounds include Viscoat # 195, Copper # 230, Copper # 260, Copper # 335HP, Copper # 540, Copper # 700 NOD, N, NPG (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

Among the above-mentioned compounds having a polymerizable double bond, polyfunctional (meth) acrylate compounds are preferable, polyfunctional methacrylate compounds are more preferable, and polyethylene glycol dimethacrylate , And polypropylene glycol dimethacrylate are more preferable, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferable.

The content of the curable compound (C) is preferably 10 parts by mass to 3000 parts by mass, more preferably 50 parts by mass to 2000 parts by mass, per 100 parts by mass of the component (A). When the content of the curable compound (C) is within the above range, the adhesion of the water entrapment body of the embodiment of the present invention formed with the composition for forming a water entrapment body of the present embodiment to the substrate can be effectively enhanced.

≪ Other optional components >

The water entrapment body forming composition of the embodiment of the present invention may contain at least one other component selected from the radical polymerization initiator (D), the fine particles (E) and additives, if necessary, within the range that does not impair the effect of the present invention . The other optional components may be used singly or in combination of two or more. The radical polymerization initiator (D) and the fine particles (E) may be referred to as component (D) and component (E), respectively.

[Radical polymerization initiator (D)]

The water entrapment body forming composition of the embodiment of the present invention may further contain a radical polymerization initiator (D). The radical polymerization initiator (D) means a compound which generates a radical by an actinic ray, heat, acid or base, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator. By containing the radical polymerization initiator (D), for example, the alcohol compound and the metal alkoxide compound formed by the hydrolysis reaction represented by the above-mentioned chemical reaction formula are efficiently immobilized and remain in the water entrapment body formed with the composition It becomes easy.

In the composition for forming a water entrapment body of the embodiment of the present invention, the radical polymerization initiator (D) may be used singly or in combination of two or more kinds.

Examples of the thermal radical polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvalero Nitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis Azobis [N- (2-propenyl) 2-methylpropionamide], 1 - [(1-cyano- 1- methylethyl) azo] formamide, 2,2 ' Azo compounds such as azobis (N-butyl-2-methylpropionamide) and 2,2'-azobis (N-cyclohexyl-2-methylpropionamide);

t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like. Of these, azo compounds are preferable as thermal radical polymerization initiators, and dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (N-butyl- ), And 2,2'-azobis (N-cyclohexyl-2-methylpropionamide) are more preferable.

V-60, V-40, V-096, V-30, VAm-110 and VAm-111 (above, Manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of commercially available products of the above-mentioned peroxides include PERBUTYL (registered trademark) Z, PERHEXA (registered trademark) 25B (manufactured by Nichiyu) and the like.

Examples of the aforementioned photo radical polymerization initiator include a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, Compounds,? -Diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, imidosulfonate compounds, and the like. Among them, the photo radical polymerization initiator is preferably at least one selected from the group consisting of an acylphosphine oxide compound, a thioxanthone compound, an acetophenone compound, a nonimidazole compound, a triazine compound, and an O-acyloxime compound It is preferable that the material contains a species.

Examples of the aforementioned acylphosphine oxide compound include 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like desirable.

Examples of the aforementioned thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Dichlorotioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

Examples of the aforementioned acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- (4-morpholinophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- .

Examples of the aforementioned imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like. When a non-imidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination because it can improve the sensitivity. The hydrogen donor means a compound capable of donating a hydrogen atom to a radical generated from a nonimidazole compound by exposure. Examples of the hydrogen donor include mercapane-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole;

And amine hydrogen donors such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. In the present embodiment, the hydrogen donors may be used singly or in combination of two or more, but it is preferable to use a combination of at least one mercaptan-based hydrogen donor and at least one amine-based hydrogen donor to improve the sensitivity It is preferable from the viewpoint of being able to do.

Examples of the above triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, and the like.

Examples of the aforementioned O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O- benzoyloxime) Ethyl-6- (2-methyl-4-tetrazol-3-yl) (9-ethyl-6- {2-methyl-4- (2,2-dimethylethyl) Dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime).

As examples of the photo radical polymerization initiator, 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of commercial products of the above-mentioned photo radical polymerization initiators include Irgacure (registered trademark) 184, Copper 369, Copper OX01, Copper OX02, Copper 819, Copper 651, Copper 500, Copper 819, Copper 907, Darocure (registered trademark) 1116, Copper 1173, Copper 4265, Copper TPO, Lucirin (registered trademark) TPO (above), BASF (registered trademark) (Manufactured by UCB), Esacure (registered trademark) KIP150, copper KIP65LT, copper KIP100F, copper KT37, copper KT55, copper KTO46, copper KIP75 / Manufactured by Lamberti Co., Ltd.).

The content of the radical polymerization initiator (D) is preferably 0.05 parts by mass to 15 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, per 100 parts by mass of the component (A). By setting the content of the radical polymerization initiator (D) within the above range, the desired radical polymerization reaction can be promptly advanced.

[Particulate (E)]

The composition for forming a water entrapment body of the embodiment of the present invention may further contain fine particles (E). The fine particles (E) are components for imparting light scattering property to the water entrapment body of the embodiment of the present invention formed using the water entrapment body forming composition of the present embodiment. Therefore, the fine particles (E) are preferably light scattering particles. The composition for forming a water entrapment body of the present embodiment contains such fine particles to improve the heat resistance and the light extraction efficiency.

The fine particles (E) are not particularly limited as long as they have an effect of scattering and extracting light formed by, for example, an organic EL element, and may be organic particles or inorganic particles.

Examples of the organic particles include polymethylmethacrylate beads, acryl-styrene copolymer beads, melamine resin beads, polycarbonate beads, polystyrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde condensate beads . As the inorganic particles, SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ and Sb ₂ O ₃ are used. These may be used alone or in combination of two or more.

As commercially available products of the fine particles (E), for example, RTTCHN15WT% -E06 manufactured by CI Harmonization Company, TS-149 manufactured by Teika Corporation, TIPA15WT% -X480 manufactured by CI Harmonized Company, N-SOL- 101-20PM or the like can be used. OPTOLAKE (registered trademark) 6320Z manufactured by Nikkiso Catalysts Co., Ltd., NanoUse (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Industries, Zirconia SZR-K manufactured by Sakaisan Chemical Co., ZR-010 can be used.

In the composition for forming a water entrapment body of the present embodiment, the fine particles (E) preferably have an average particle diameter of 50 nm to 500 nm in the moisture entrapment forming composition and a particle diameter of 600 nm to the total amount of the fine particles (E) Or more of the particles is 20% by volume or less.

When the average particle diameter of the fine particles (E) is less than 50 nm, a sufficient scattering effect is not exhibited, and the refractive index of the formed water entrapping body is affected, which is not preferable. If it is larger than 500 nm, scattering angle becomes narrow even if the scattering intensity (haze value) is high, so effective scattering can not be obtained and the light extraction efficiency is lowered, or the change due to the wavelength of the light extraction efficiency increases, It is easy and sometimes not desirable. More preferably, it is 50 nm to 300 nm.

If the content of particles having a particle diameter of 600 nm or more with respect to the total amount of the fine particles (E) is more than 20% by volume, the change in the light extraction efficiency due to the wavelength becomes large and the color tone is liable to change. Further, since the surface roughness of the formed water entrapment body becomes large, there is a possibility that a film thickness deviation or protrusion of the water entrapment body occurs. The content of the particles of 600 nm or more is more preferably 15 vol% or less.

In the present invention, the "average particle diameter" and "particle diameter" of the fine particles (E) are different from the average primary particle diameter described later, Forming composition. These can be obtained by optical microscopy or by dynamic light scattering. The reason for distinguishing the average primary particle diameter from the average primary particle diameter is that, even when scattering particles having the same average primary particle size are used, the average particle size and the particle size distribution are determined by the dispersion state of the fine particles in the water entrapment body- This is because there are cases in which they are different. The " average particle diameter " is the value of the dispersed particle diameter at 50 volume% of the measurement sample, and the content of particles having a particle diameter of 600 nm or more is the volume percentage of the particle diameter at least 600 nm in the dispersion particle diameter of the measurement sample . These can be measured by "Nanotrac (registered trademark) UPA" manufactured by Nikkiso Co., Ltd. as a dynamic light scattering method.

The particle size distribution of the fine particles (E) preferably has a coefficient of variation of 30% or less. The " variation coefficient " refers to a percentage of a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter, and is an index of the magnitude of the deviation relative to the average particle diameter. If the coefficient of variation is larger than 30%, the change due to the wavelength of the light extraction efficiency becomes large, and the color tone is liable to change, which is not preferable. More preferably, the coefficient of variation is 20% or less.

As the method of using the fine particles (E), it is preferable to use a dispersion dispersed in a solvent in advance.

As a method of dispersing the fine particles (E), a method using a dispersing agent that is suitable for the surface state of the fine particles and using a dispersing machine is preferable.

Examples of the above-mentioned dispersing machine include a paint conditioner (manufactured by Red Devil), a ball mill, a sand mill (Dyno-Mill manufactured by Shinmaru Enterprise Co., Ltd.), Atrito, Pearl mill (Registered trademark) "manufactured by M Technica Co., Ltd.), a wet jet mill (" Genus (registered trademark) PY "manufactured by JUNUS Co., Ltd.) Super Apex Mill " and " Ultra Apex Mill " manufactured by Kotobuki Kogyo Co., Ltd.), " Nanomizer (registered trademark) &Quot;) can be used.

Here, when the medium is used in the above-mentioned dispersing machine, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads or the like. Regarding dispersion, two or more kinds of dispersion machines or two or more kinds of media having different sizes may be used, respectively, and they may be carried out stepwise.

The average particle diameter and particle size distribution of the fine particles (E) can be adjusted to a suitable range by appropriately adjusting dispersion conditions such as a dispersion medium, a dispersion medium, a dispersion time, and a dispersing agent in the case of inorganic particles. Further, in the case of the organic particles, the conditions can be adjusted by the conditions of the polymerization such as the polymerization temperature and the polymerization composition, or the dispersion conditions such as the dispersing machine, dispersion medium, dispersion time and dispersing agent.

The amount of the fine particles (E) to be used is preferably 1% by mass to 25% by mass, and more preferably 1% by mass to 20% by mass, in the water entrapping body forming composition. When the content is less than 1% by mass, sufficient scattering effect may not be exhibited. If it exceeds 25% by mass, the particles tend to flocculate with each other, and the surface roughness of the formed water entrapment body may increase.

[additive]

The moisture trapping body forming composition of the embodiment of the present invention may contain an additive agent as required. Specifically, there may be exemplified a sensitizer, a curing accelerator, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent and a surfactant.

≪ Preparation method of water entrapment body forming composition >

The water entrapment forming composition of the present invention is prepared by mixing the above-mentioned components (A), (B) and (C) and mixing the components (D), (E) And the like.

The moisture trapping body forming composition of the embodiment of the present invention is used for forming a water entrapment body used in an electronic device in which moisture may be deteriorated, particularly for forming a water entrapping body constituting an organic EL element, And can be suitably used. For example, after a water entrapment body is formed using the moisture trapping body forming composition of the present embodiment, and an organic EL element including the water entrapment body is formed (for example, encapsulated), at least one of irradiation and heating is performed The water trapping ability of the water entrapment body of the present embodiment can be exhibited.

[Moisture trapped body]

The water entrapment body of the embodiment of the present invention is formed using the water entrapment body forming composition of the embodiment of the present invention as described above.

As the method for forming the water entrapment body of the present embodiment, a method may be used in which the water trap body forming composition of the embodiment of the present invention described above is used and a coating film is formed on a substrate such as glass, , A method of heating, a method of forming by curing by a method of irradiating and heating, and the like.

The above-mentioned radiation is not particularly limited as long as it can cure the coating film of the moisture trapping body forming composition, but UV (ultraviolet) light is preferable. For example, a coating film of the moisture trapping body forming composition can be cured by ultraviolet irradiation (for example, 500 to 15000 mJ / cm 2) using a high-pressure mercury lamp.

The heating temperature of the aforementioned heating method is preferably 30 to 200 캜, more preferably 50 to 150 캜. The heating time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours.

The water entrapment body of the present embodiment is formed of the water entrapment body forming composition of the embodiment of the present invention described above, and is composed of (A) at least one member selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound (B) at least one compound selected from the group consisting of an acid generator and a base generator, and (C) a curing compound.

In the following description, at least one compound selected from the group consisting of (A) a compound having a hydrolyzable group and a hydrolyzate of the compound is also referred to as (A) compound, (B) an acid generator and a base (B), and (C) a curable compound is also referred to as a (C) compound.

Since the water entrapment body of the present embodiment is formed of the water entrapment body forming composition of the embodiment of the present invention as described above, the compound (A) is a water entrapment agent (A) (A)). That is, the compound having a hydrolyzable group in the compound (A) is contained in the water entrapment forming composition as the water entrapping agent (A). Likewise, the compound (B) contained in the moisture trapping material of the present embodiment is in accordance with the acid / base generator (B) (component (B)) of the moisture trapping material forming composition of the embodiment of the present invention. The compound (C) contained in the water entrapment body of the present embodiment conforms to the curing compound (C) (component (C)) of the water entrapment body forming composition of the embodiment of the present invention.

Therefore, examples of the compound having a hydrolysable group as the compound (A) are the same as those of the water trapping agent (A) of the composition for forming a water entrapping body, and examples of the compound (B) Is the same as the base generator (B), and examples of the compound (C) are the same as the curing compound (C) of the composition for forming a water entrapment body.

As described above, in the composition for forming a water entrapment body according to the embodiment of the present invention, when the acid-generating agent (B1) is contained, the water capturing agents (A1) to (A3) Is used. On the other hand, in the composition for forming a water entrapment body of the embodiment of the present invention, in the case of containing the nucleating agent (B2), at least one of water entrapping agents (A2) Paper is used.

More specifically, in the water entrapment body of the present embodiment, the compound (A) is a compound represented by the formula (A1-1), the compound represented by the formula (A1-2) (A2) compound selected from (A2) at least one compound selected from compounds represented by the following general formula (3) (also referred to as (A1) compound), (A2) at least one compound selected from carbonic acid anhydride and carbonic acid compound , (A3) at least one compound selected from a compound represented by the formula (A3-1), a compound represented by the formula (A3-2) and a compound represented by the formula (A3-3) , And the compound (B) is preferably at least one selected from the group consisting of an acid generator.

As another example, in the water entrapment body of the present embodiment, the compound (A) is at least one selected from the group consisting of the above-mentioned (A2) compound and the above-mentioned (A3) Is preferably a nucleating agent:

Wherein R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or a group having 1 to 18 carbon atoms R ³ , R ⁴ and R ⁷ may be combined with a carbon atom to which they are directly bonded to form a cyclic structure, n is 0 or an integer of 1 to 18, * represents a bonding position ;

In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms;

R ⁸ is each independently an organic group having 3 to 30 carbon atoms;

In the formula (A1-3), the formula R ⁸ is the same as the formula (A1-2);

[In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom;

R ²¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group;

R ²² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxirane group, a 3,4-epoxycyclohexyl group, or a mercapto group;

p is an integer from 0 to 6;

r is an integer of 0 to 2, and s is an integer of 1 to 30;

The compound represented by the formula (A1-3) in the compound (A) can be obtained by reacting the compound represented by the formula (A1-1) with the compound represented by the formula And a hydrolysis product of a compound represented by the formula (A1-2).

The carbonic acid anhydride, which is the compound (A), is a carbonic acid anhydride of the aforementioned water trapping agent (A2). The carbonic acid compound in the compound (A) is a hydrolysis product of the carbonic acid anhydride, as described for the action and effect of the water entrapment forming composition of the embodiment of the present invention.

The compound represented by the formula (A3-3) in the compound (A) can be obtained by reacting the compound represented by the formula (A3-1) and the compound represented by the formula (A3-1) as described in the working effect of the water entrapment forming composition of the embodiment of the present invention A3-2). ≪ / RTI >

The water entrapment body of the embodiment of the present invention is characterized in that at least one kind of compound selected from the group consisting of the water entrapping agents (A1) to (A3) and the hydrolysis products of the water entrapment body forming composition of the embodiment of the present invention .

Further, the water entrapment body of the present embodiment may be formed of the moisture trapping body forming composition of the embodiment of the present invention described above, and may contain (D) a radical polymerization initiator. When the moisture trapping material of the present embodiment contains (E) fine particles, the radical polymerization initiator (D) thereof can be added to the radical polymerization initiator (D) (component (D)) of the moisture trapping body forming composition of the embodiment of the present invention To follow. Therefore, examples of the radical polymerization initiator (D) are the same as those of the component (D) of the moisture entrapment forming composition. By containing the radical polymerization initiator (D) in the water entrapment body of the present embodiment, the product of the hydrolysis reaction such as an alcohol compound is efficiently immobilized in the water entrapment body, and it is easy to stay.

In addition, the water entrapment body of the present embodiment is formed of the water entrapment body forming composition of the embodiment of the present invention described above, and may contain (E) fine particles. When the moisture trapping material of the present embodiment contains (E) fine particles, the (E) fine particles are in accordance with the fine particles (E) (component (E)) of the water trapping body forming composition of the embodiment of the present invention. Accordingly, examples of the (E) fine particles are the same as the component (E) of the moisture entrapment forming composition. The moisture trapping material of the present embodiment contains (E) fine particles to improve the heat resistance and can be applied to the organic EL device to improve the light extraction efficiency.

The moisture trapping body of the embodiment of the present invention described above can efficiently remove moisture in an electronic device such as an organic EL element to be applied and can consume moisture in the element even after the formation.

The water entrapment body of the present embodiment hardly generates highly volatile decomposition products such as low molecular alcohol even in the state of capturing moisture. For example, when it is used in an organic EL device or the like, Occurrence of dark spots due to adhesion of decomposition products can be suppressed. That is, the moisture trapping body of the embodiment of the present invention can be suitably used particularly for an organic EL element.

[Electronic Devices]

The moisture trapping body forming composition of the embodiment of the present invention is used in the constitution of an electronic device according to the embodiment of the present invention in which water entrapment bodies are formed and moisture may deteriorate the characteristics. As the electronic device according to the embodiment of the present invention, any electronic device may be used as long as the moisture content is an electronic device that may degrade the characteristics. Examples of such an electronic device include an organic EL device and a liquid crystal display device. In the case of an organic EL device, for example, a highly reliable organic EL lighting device and an organic EL display device can be constituted.

When the organic EL device of the embodiment of the present invention is provided with the moisture trapping body of the embodiment of the present invention, when the moisture trapping body is formed of the moisture trapping body forming composition of the embodiment of the present invention, Can be removed. Further, the moisture trapping body of the embodiment of the present invention can absorb moisture in the element for a long period of time even after its formation, and therefore deterioration of the element due to moisture can be suppressed.

≪ Organic EL device &

Next, an organic EL device according to an embodiment of the present invention will be described with reference to the drawings.

1 is a cross-sectional view schematically showing a first example of an organic EL device according to an embodiment of the present invention.

An organic EL element 100 as a first example of an organic EL element according to an embodiment of the present invention shown in Fig. 1 houses an organic EL layer 10 and an organic EL layer 10 to shield from the outside air And a moisture trapping body 30 formed in the structure 20. As shown in Fig. The water entrapment body 30 is formed using the water entrapment body forming composition of the embodiment of the present invention described above. The structure 20 also includes a substrate 22 or a sealing substrate 24 as a substrate for devices for supporting the organic EL layer 10 and a sealing material 26.

The organic EL layer 10 of the organic EL element 100 is not particularly limited in structure but may be a structure in which an organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other. An anode / an organic light emitting layer / a cathode, or the like. If necessary, a charge (hole) injecting layer or a charge (hole) transporting layer can be formed between the anode and the organic light emitting layer, and an electron injecting layer or an electron transporting layer is formed between the cathode and the organic light emitting layer can do. The organic EL layer 10 is disposed on the substrate 22 of the structure 20 as shown in Fig.

When the organic EL element 100 is a top emitter structure, the organic EL element 10 may have a bottom surface or a top emitter surface, ) Electrode, an organic luminescent layer, and a translucent or semi-transmissive front electrode serving as a cathode are arranged on the substrate 22 in this order.

In this case, the back electrode of the organic EL layer 10 preferably has light reflectivity. As a material of the back electrode, metals, alloys, conductive metal oxides, other conductive compounds, and mixtures thereof can be used.

As a specific example of the material of the back electrode of the organic EL layer 10,

Alkali metals (for example, Li, Na and K) and fluorides thereof;

Alkaline earth metals (such as Mg and Ca) and fluorides thereof;

Gold, silver, lead, aluminum, sodium-potassium alloy, and mixed metal containing them;

Lithium-aluminum alloys and mixed metals containing them;

LiF / Al alloys and mixed metals containing them;

Magnesium-silver alloys and mixed metals containing them;

Indium, and rare-earth metals such as ytterbium.

Preferably, the material has a work function of 4 eV or less, more preferably aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof.

The film thickness of the back electrode of the organic EL layer 10 can be appropriately selected depending on the material, but is preferably 100 nm to 1 占 퐉. The rear electrode may be formed by electron beam deposition, sputtering, resistance heating deposition, or coating. At this time, the metal may be deposited singly or two or more components may be deposited at the same time. In addition, a plurality of metals may be simultaneously deposited to form an alloy electrode, or a previously adjusted alloy may be deposited.

In addition, the material of the organic light emitting layer of the organic EL layer 10 can be a material for injecting holes from an anode or the like at the time of applying an electric field, a function for injecting electrons from a cathode or the like, And a material capable of forming a layer having a function of emitting light by providing a site for recombination of holes and electrons.

The material of the organic light-emitting layer of the organic EL layer 10 can be selected from the group consisting of benzooxazole derivatives, benzoimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, , Naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, arzazine derivatives, pyrrolidine derivatives, cyclopentadiene derivatives, bisstyryl anthracene derivatives, quinacridone derivatives, Various metal complexes such as pyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidine compounds and metal complexes of 8-quinolinol derivatives or rare earth complexes;

And

And polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene.

Specific examples of the luminescent material to be the organic luminescent layer of the organic EL layer 10 are set forth below, but the present invention is not limited to those specifically illustrated below.

Blue light emission is obtained by using, for example, perylene, 2,5,8,11-tetra-t-butyl perylene (TBP) and 9,10-diphenylanthracene derivatives as a guest material. In addition, styrylarylene derivatives such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPVBi), 9,10-di-2-naphthylanthracene (DNA) And bis (2-naphthyl) -2-tert-butyl anthracene (t-BuDNA). Further, a polymer such as poly (9,9-dioctylfluorene) may be used.

The luminescence of green can be obtained by using coumarin-based coloring matters such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinate] picolinate iridium (FIrpic) Acetylacetonate iridium (Ir (ppy) (acac)) or the like as a guest material. Further, tris (8-hydroxyquinoline) aluminum (Alq _3), BAlq, Zn (BTZ) and bis (2-methyl-8-quinolinolato) gallium chloro (Ga (mq) ₂ Cl), etc. of the metal complex . Further, a polymer such as poly (p-phenylenevinylene) may be used.

The light emission from the orange color to the red emission can be carried out in the same manner as in Example 1 except that rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6- Pyran (DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] (2-thienyl) pyridinate] acetylacetonate iridium (Ir (thp) ₂ (acac)) and bis (2-phenylquinolinate) acetylacetonate Iridium (Ir (pq) (acac)) or the like as a guest material. Can also be obtained from metal complexes such as bis (8-quinolinolato) zinc (Znq ₂ ) and bis [2-cinnamoyl-8-quinolinolate] zinc (Znsq ₂ ). Further, a polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

The white light emission is an element using the same tunnel injection as the one in which the energy level of each layer of the organic EL laminate structure is defined and light is emitted by tunnel injection (European Patent Publication No. 0390551) (Japanese Unexamined Patent Application, First Publication No. Hei 2-220390 and Japanese Unexamined Patent Application, First Publication No. Hei 2-216790), a light emitting layer having a two-layer structure is disclosed (Japanese Unexamined Patent Publication No. 4-51491), a blue light emitting body (fluorescent peak 380 to 480 nm) and a green light emitting body (480 to 580 nm) are laminated, (Japanese Unexamined Patent Publication (Kokai) No. 6-207170), a blue light emitting layer containing a blue fluorescent dye, a green light emitting layer having a region containing a red fluorescent dye, and a green fluorescent substance containing a green fluorescent substance The configuration ( And the like can be present Laid-Open Patent Publication No. Hei 7-142169).

The thickness of the organic light-emitting layer of the organic EL layer 10 is not particularly limited, but is preferably 10 nm to 500 nm. Each layer may be a single layer structure or a multi-layer structure of the same composition or different composition.

The method of forming the organic light emitting layer of the organic EL layer 10 is not particularly limited and may be any one of a resistance heating deposition method, an electron beam deposition method, a sputtering method, a molecular stacking method, a coating method (spin coating method, casting method, , And LB (Langmuir Blodgett) method are used. Preferably a resistance heating deposition method and a coating method.

It is preferable that the front electrode of the organic EL layer 10 has translucency or translucency when the organic EL element 100 has a top emission structure as described above.

As the material of the light-transmitting or semi-light-transmitting front electrode of such organic EL layer 10, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used.

As a specific example of the material of the light-transmitting or semi-light-transmitting front electrode of the organic EL layer 10,

Conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO);

Metals such as gold, silver, chromium, and nickel;

Other inorganic conductive materials such as copper iodide and copper sulfide;

Organic conductive materials such as polyaniline, polythiophene, PEDOT / PSS, and polypyrrole;

And mixtures or laminates thereof.

Among the front electrodes of the organic EL layer 10 described above, ITO is preferably used as the conductive metal oxide, particularly in terms of productivity, high conductivity, and light transmittance.

The front electrode of the organic EL layer 10 may be made of a transparent electrode by laminating metals and ITO in order to control the injecting property of electrons into the organic light emitting layer while maintaining light transmittance. Here, the thickness of the extremely thin metal is preferably 0.1 nm to 20 nm from the viewpoint of maintaining the light transmittance. In addition, as the metals referred to herein,

Alkali metals (e.g., Li, Na, and K, etc.) and fluorides thereof;

Alkaline earth metals (such as Mg and Ca) and fluorides thereof;

Gold, silver, lead, aluminum, sodium-potassium alloy, and mixed metal containing them;

Lithium-aluminum alloys and mixed metals containing them;

LiF / Al alloys and mixed metals containing them;

Magnesium-silver alloys and mixed metals containing them;

Indium, and rare-earth metals such as ytterbium.

Among the above examples, the above-mentioned metals are preferably aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof.

The film thickness of the front electrode can be appropriately selected depending on the material, but is usually preferably about 50 nm to 300 nm.

As a method of forming the front electrode, a method such as electron beam method, sputtering method, resistance heating deposition method, chemical reaction method (sol-gel method), and application of a melt or dispersion are used. The formed front electrode is subjected to an etching treatment as desired to form a pattern. It is also possible to lower the driving voltage of the organic EL element or increase the luminous efficiency by cleaning or other treatments. For example, when ITO is used for the front electrode, UV-ozone treatment and the like are effective.

When the organic EL layer 10 has a hole injecting layer or a hole transporting layer between the anode and the organic light emitting layer, their materials include a function of injecting holes from the anode, a function of transporting injected holes, And a function of blocking the electrons that have been generated. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Wherein the aromatic diamine compound is at least one selected from the group consisting of a styryl anthracene derivative, a styrenthracene derivative, a fluorenone derivative, a hydrazone derivative, a stilbene derivative, a silazane derivative, an aromatic tertiary amine compound, , Poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive high molecular oligomers such as polythiophene.

When the organic EL layer 10 has an electron injecting layer and an electron transporting layer between the cathode and the organic light emitting layer, the material of the electron injecting layer and the electron transporting layer may have a function of injecting electrons from the cathode, a function of transporting electrons , Or a barrier that has holes to be injected from the anode. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimide derivatives, fluorenylidene Methane derivatives, distyrylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, silole derivatives, phthalocyanine derivatives, and metal complexes of 8-quinolinol derivatives;

And various metal complexes typified by metal complexes having metal phthalocyanine, benzoxazole and benzothiazole as ligands.

The film thickness of the hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer of the organic EL layer 10 is not particularly limited, but is preferably 10 nm to 500 nm. Each layer may be a single layer structure or a multi-layer structure of the same composition or different composition.

The method of forming these layers of the organic EL layer 10 is not particularly limited, and examples thereof include resistance heating deposition, electron beam deposition, sputtering, molecular deposition, coating (spin coating, , And LB (Langmuir Blodgett) method are used. Preferably a resistance heating deposition method and a coating method.

In the organic EL device 100 having the organic EL layer 10 having the structure described above, the moisture trapping body 30 formed in the structure 20 is separated from the organic EL layer 10 as shown in FIG. 1 Respectively.

The structure 20 of the organic EL element 100 includes a substrate 22, a sealing material 26 formed on the periphery of the organic EL layer 10 in the substrate 22, And a sealing substrate 24 fixed to the substrate 22. The organic EL layer 10 is encapsulated by the substrate 22, the sealing substrate 24, and the sealing material 26. The inside of the organic EL element 100 has a hollow structure and may be filled with an inert gas so as not to deteriorate the organic EL layer 10. [

The sealing material 26 is a sealing material formed of an adhesive composition. As the substrate 22 of the organic EL element 100, a glass substrate or the like can be mentioned, and as the sealing substrate 24, a structure made of glass or the like can be given. The sealing material 26 fixes the sealing substrate 24 to the substrate 22 and seals the organic EL layer 10 between the sealing substrate 24 and the substrate 22. The structure of the structure 20 is not particularly limited as long as it can house the organic EL layer 10 and seal it with the sealing material 26. [

For example, when the organic EL device 100 is manufactured, the substrate 22 and the sealing substrate 24 are adhered to each other by a coating film composed of an adhesive composition, and then the film is cured by irradiating and / or heating The sealing material 26 can be formed and the organic EL layer 10 can be sealed in the sealing space.

The moisture trapping body 30 formed in the structure 20 captures moisture in the sealed space in which the organic EL layer 10 is sealed and can be efficiently removed. The structure and arrangement of the moisture trapping body 30 are not particularly limited. For example, as in the case of the organic EL element 100 shown in Fig. 1, on the sealing substrate 24 . The moisture trapping body 30 may be disposed on the side surface of the organic EL layer 10 or the sealing material 26 in the sealing space. The water entrapment body 30 may be laminated on the organic EL layer so as to be in close contact with the organic EL layer 10 and may be arranged to fill the entire encapsulation space in the structure 20 without any gap as described later There may be.

The organic EL device 100 having the above structure is provided with the moisture trapping body 30 so that moisture in the element is removed. Then, the organic EL element 100 can suppress deterioration of light emission characteristics such as luminance and luminous efficiency due to moisture. The organic EL element 100 can constitute, for example, a highly reliable organic EL lighting apparatus.

The organic EL device 100 can also constitute an organic EL display device. The organic EL element 100 uses, for example, a TFT substrate on which a thin film transistor (TFT) as a switching element is formed for each pixel arranged in a matrix, as a substrate 22, and a plurality of An organic EL display device of an active matrix type can be constructed by forming the organic EL layer 10 in a matrix shape corresponding to the pixels.

Hereinafter, another example of the organic EL device according to the embodiment of the present invention will be described.

2 is a cross-sectional view schematically showing a second example of the organic EL device according to the embodiment of the present invention.

The organic EL device 200 shown in Fig. 2, which is a second example of the organic EL device according to the embodiment of the present invention, has the water entrapment body 130 formed in the structure 20. The water trapping body 130 is formed using the water trapping body forming composition of the embodiment of the present invention described above.

The organic EL device 200 differs from the organic EL device 100 shown in Fig. 1 in that the moisture trapping body 130 formed in the structure 20 is formed in close contact with the organic EL layer 10. In the organic EL device 200 shown in Fig. 2, the same components as those of the organic EL device 100 shown in Fig. 1, such as the organic EL layer 10, are denoted by the same reference numerals, .

In the organic EL element 200, the moisture trapping body 130 can remove water at the time of formation and prevent moisture from entering the organic EL layer 10 due to its hygroscopicity after formation . In addition, since the moisture trapping body 130 is formed to be in close contact with the organic EL layer 10, the organic EL layer 10 can also be protected. The organic EL element 200 can constitute, for example, a highly reliable organic EL lighting apparatus.

3 is a cross-sectional view schematically showing a third example of the organic EL device according to the embodiment of the present invention.

The organic EL device 300 shown in Fig. 3 differs from the organic EL device 100 shown in Fig. 1 in that a gas barrier film 40 covering the entire surface of the organic EL layer 10 is formed , And so on.

The gas barrier film 40 is formed to prevent water and oxygen from contacting the organic EL layer 10. [ The gas barrier film 40 is not particularly limited and conventionally known ones can be used. For example, a film formed by alternately stacking an organic film and an inorganic film can be given.

As the gas barrier film 40, there can be mentioned, for example, the specifications of U.S. Patent Application Publication No. 2005/202646, U.S. Patent Application Publication No. 2005/176181, U.S. Patent Application Publication No. 2003/203210, U.S. Patent Application Publication No. 2009 / 208754 specification, International Publication No. 2003/028903 pamphlet, International Publication No. 2008/094352 pamphlet, International Publication No. 2009/009306 pamphlet, International Publication No. 2010/077544 pamphlet and the like.

The organic EL element 300 is provided with the gas barrier film 40 together with the moisture trapping body 30 so that moisture in the element is removed and the contact of moisture with the organic EL layer 10 can be further reduced have. The organic EL element 300 can constitute, for example, a highly reliable organic EL lighting apparatus.

4 is a cross-sectional view schematically showing a fourth example of the organic EL device according to the embodiment of the present invention.

The organic EL device 400 shown in Fig. 4 differs from the organic EL device 200 shown in Fig. 2 in that a gas barrier film 40 covering the entire surface of the organic EL layer 10 is formed , And so on. The gas barrier film 40 is the same as that provided by the organic EL element 300 shown in Fig.

The organic EL element 400 is provided with the gas barrier film 40 together with the moisture trapping body 130 so that moisture in the element is removed and contact of moisture with the organic EL layer 10 can be further reduced have. The organic EL element 400 can constitute, for example, a highly reliable organic EL lighting apparatus.

5 is a cross-sectional view schematically showing a fifth example of the organic EL device according to the embodiment of the present invention.

The organic EL device 500 shown in Fig. 5 has the same structure as that of the organic EL device 400 shown in Fig. 4 except that, on the organic EL layer 10, a moisture trapping body And the gas barrier film 40 covering the entire surface of the moisture trapping body 30 and the side surface of the organic EL layer 10 is formed on the surface of the water trap 30, same.

The gas barrier film 40 is the same as that provided by the organic EL elements 300 and 400 shown in Figs.

The organic EL element 500 is provided with the gas barrier film 40 together with the water entrapment bodies 30 and 130 so that moisture in the element is removed and moisture contact with the organic EL layer 10 is further reduced can do. The organic EL device 500 can constitute, for example, a highly reliable organic EL lighting device.

Example

Hereinafter, embodiments of the present invention will be described in detail on the basis of examples, but the present invention is not limited to these examples.

< ¹ H-NMR measurement>

¹ H-NMR was measured at 25 캜 using a nuclear magnetic resonance apparatus (JNM-ECS 400 (400 MHz), manufactured by Nippon Denshi Co., Ltd.).

&Lt; Synthesis of water entrapment agent (A1) >

As the water trapping agent (A1) contained in the water trap body forming composition of the embodiment of the present invention, the compound having the structural moiety represented by the formula (A1-1) or the compound represented by the formula (A1-2) AO-1) to (AO-12) compounds. For a method of synthesizing them, reference can be made to the pamphlet of International Publication (WO) 01/021611. Hereinafter, the (AO-1) to (AO-12) compounds are referred to as a water capturing agent (AO-1) to a water capturing agent (AO-12), respectively.

[Synthesis Example 1] Synthesis of water entrapping agent (AO-1)

53.0 parts by mass of methyl orthoformate, 80.0 parts by mass of 2-butyl-2-ethyl-1,3-propanediol, 17.0 parts by mass of pentaerythritol, And 0.5 parts by mass of a 90 wt% aqueous solution of formic acid were placed, and the resulting methanol was kept at about 85 캜 for 1 hour while distilling off methanol produced by an alcohol exchange reaction. Thereafter, the temperature was raised to 175 占 폚 over 2 hours, and 46.5 parts by mass of methanol was recovered to obtain a water entrapping agent (AO-1) as a colorless transparent viscous polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-1) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (24H, m), delta 5.22 (4H, m), delta 1.10 to 1.60 (32H, m), delta 3.34 to 4.0 s).

[Synthesis Example 2] Synthesis of water entrapping agent (AO-2)

The following water capturing agent (AO-2) was obtained from methyl orthoformate, 1,2-dodecanediol, pentaerythritol and 90 wt% formic acid aqueous solution in the same manner as in the aforementioned water capturing agent (AO-1).

The results of ¹ H-NMR measurement of the water entrapment agent (AO-2) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (8H, m),? 3.90 (4H, m),? 3.95 to 4.05 (8H, m),? , [delta] 5.80 (8H, s), [delta] 6.30 (4H, s).

[Synthesis Example 3] Synthesis of water entrapping agent (AO-3)

The following water trapping agent (AO-3) was obtained from methyl orthoformate, butyl alcohol, pentaerythritol and 90 wt% formic acid aqueous solution in the same manner as the water trapping agent (AO-1).

The results of ¹ H-NMR measurement of the water entrapment agent (AO-3) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; m),? 3.40 (12H, m),? 3.60 to 3.80 (8H, m),? 0.85 (12H, s),? 1.25 to 1.30 , delta 3.95-4.00 (8H, m), delta 4.20-4.30 (4H, m), delta 5.80 (8H, s), delta 6.25 (4H, s).

[Synthesis Example 4] Synthesis of water entrapping agent (AO-4)

(AO-4) was obtained from methyl orthoformate, 2-butyl-2-ethyl-1,3-propanediol, trimethylol propane and 90% by weight formic acid aqueous solution in the same manner as the water entrapment agent (AO- ).

The results of ¹ H-NMR measurement of the water entrapment agent (AO-4) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (2H, q),? 1.60 to 1.75 (8H, m),? 3.80 (4H, d),? 3 .85 (8H, q),? 5.80 (2H, s),? 6.05 (3H, s).

[Synthesis Example 5] Synthesis of water entrapping agent (AO-5)

53.0 parts by mass of methyl orthoformate, 80.0 parts by mass of 2-butyl-2-ethyl-1,3-propanediol, and 80.0 parts by mass of methacrylic acid hydroxyester 65.0 And 0.5 parts by mass of a 90 wt% aqueous solution of formic acid were placed, and the methanol produced by the alcohol exchange reaction was distilled off and the mixture was stored at about 85 ° C for 1 hour. Thereafter, the temperature was raised to 175 캜 over 2 hours to remove methanol, thereby obtaining a water-capturing agent (AO-5) having a viscous methacryl group.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-5) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (2H, q),? 3.85 (2H, q),? 0.90 (2H, t),? 1.20-1.40 (1H, s),? 6.50 (1H, s),?

Subsequently, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 70 parts by mass of a methacrylic group-containing water trapping agent (AO-5) and 30 parts by mass of styrene were charged, and after nitrogen replacement, stirring was gently started. The temperature of the solution was raised to 70 캜, and the temperature was maintained for 5 hours to form a polymer to obtain a solution containing the water entrapping agent (AO-5-1) as a polymer. The polystyrene reduced weight average molecular weight (mW) of the water entrapping agent (AO-5-1) as a polymer was 8,000. The solid content concentration of the obtained solution was 34.1 mass%.

As a result of ¹ H-NMR measurement of the water entrapment agent (AO-5-1), it was confirmed that a peak near δ 6.40 due to the double bond of the water entrapment agent (AO-5) was lost.

[Synthesis Example 6] Synthesis of water entrapping agent (AO-6)

53.0 parts by mass of methyl orthoformate, 80.0 parts by mass of 2-butyl-2-ethyl-1,3-propanediol, 20.0 parts by mass of novolac resin (available from Guyi Chemical Co., Ltd.) as a polymerization initiator were added to a reaction apparatus equipped with a stirrer, 100.0 parts by mass of HAIHYAKU) and 0.5 parts by mass of a 90 wt% aqueous solution of formic acid were placed and maintained at about 85 占 폚 for 2 hours while distilling off methanol produced by an alcohol exchange reaction. Thereafter, the temperature was raised to 175 ° C over 2 hours to remove methanol to obtain a water entrapping agent (AO-6) as a novolak resin having a viscous orthoester.

As a result of ¹ H-NMR measurement of the water trapping agent (AO-6), it was confirmed that the peak near 5.30 of the hydroxyl group of the novolak resin as the raw material was lost.

[Synthesis Example 7] Synthesis of water entrapping agent (AO-7)

53.0 parts by mass of methyl orthoformate, 80.0 parts by mass of trimethylolpropane monoallyl ether, 17.0 parts by mass of pentaerythritol and 0.5 parts by mass of a 90% by mass formic acid aqueous solution were placed in a reactor equipped with a stirrer, a condenser, a temperature controller and a solvent recovery device , And the methanol produced by the alcohol exchange reaction was distilled off and kept at about 85 캜 for 1 hour. Thereafter, the temperature was raised to 175 DEG C over 2 hours, and 46.5 parts by mass of methanol was recovered to obtain a water trapping agent (AO-7) as a colorless transparent and viscous polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-7) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (8H, m),? 5.83 (12H, m),? 1.84 (1.5H, m),? .

[Synthesis Example 8] Synthesis of water entrapping agent (AO-8)

50.0 parts by mass of water trapping agent (AO-1) and 3.0 parts by mass of t-butoxy potassium were put in a reaction apparatus equipped with a stirrer, a condenser, a temperature controller and a solvent recovery device and stirred at 160 DEG C for 6 hours under a nitrogen atmosphere . Thereafter, 0.6 mass parts of KYOWAAD (registered trademark) 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an alkali adsorbent and treated at 120 DEG C for 1 hour. After cooling the reaction solution to room temperature, the adsorbent was separated by filtration , And a water entrapping agent (AO-8) was obtained as a colorless and transparent viscous polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-8) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (24H, d), delta 3.25-4.10 (32H, m), delta 4 (8H, m), delta 1.85 (4H, m),? 5.10 to 5.40 (4H, m),? 5.80 to 6.15 (4H, m).

[Synthesis Example 9] Synthesis of water entrapping agent (AO-9)

63.0 parts by mass of methyl orthoformate, 55.0 parts by mass of glycerin, 20.0 parts by mass of pentaerythritol and 0.5 parts by mass of a 90% by mass formic acid aqueous solution were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature control device and a solvent recovery device. Methanol was distilled off and kept at about 85 占 폚 for 1 hour. Thereafter, the temperature was raised to 175 ° C over 2 hours to recover 57.0 parts by mass of methanol, and the mixture was concentrated under the conditions of 175 ° C and 300Pa to remove volatile components. A water entrapping agent (AO-9) was obtained as a colorless transparent viscous polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-9) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; ? 3.20-4.20 (24H, m),? 4.20-4.70 (4H, m),? 5.60-6.10 (4H, m).

[Synthesis Example 10] Synthesis of water entrapping agent (AO-10)

42.5 parts by mass of methyl orthoformate, 55.3 parts by mass of glycerin, and 0.4 part by mass of a 90% by mass formic acid aqueous solution were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature control device and a solvent recovery device. Methanol produced by an alcohol exchange reaction was distilled While maintaining at 85 캜 for 2 hours. Thereafter, the temperature was raised to 150 캜 over 4 hours, and the mixture was concentrated under the condition of 300 Pa to remove volatile components. A water entrapping agent (AO-10) was obtained as a colorless transparent viscous polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-10) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; ? 3.46-4.54 (18H, m),? 5.82-6.06 (2H, m).

[Synthesis Example 11] Synthesis of water entrapping agent (AO-11)

12.7 parts by mass of methyl orthoformate, 50.2 parts by mass of OXT-101, and 0.6 parts by mass of a 90% by mass formic acid aqueous solution were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature controller and a solvent recovery device, Was distilled off and kept at about 95 캜 for 16 hours. Thereafter, the temperature was raised to 140 占 폚, and the mixture was concentrated under the condition of 300 Pa to remove volatile components. A water entrapping agent (AO-11) was obtained as a white solid polyorthoester.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-11) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (6H, d),? 4.51 (6H, d),? 5.42 (1H, , s).

[Synthesis Example 12] Synthesis of water entrapping agent (AO-12)

21.2 parts by mass of methyl orthoformate, 18.4 parts by mass of glycerin, and 1 part by mass of a 90% by mass aqueous formic acid solution were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature control device and a solvent recovery device. Methanol produced by an alcohol exchange reaction was distilled The reaction was carried out at 85 DEG C for 1.5 hours and at 90 DEG C for 1 hour. Thereafter, 25.6 parts by mass of OXT-101 was added. Methanol produced by raising the temperature to about 140 占 폚 over 6 hours was distilled off, and the mixture was concentrated under the conditions of 140 占 폚 and 300 Pa to remove volatile components. A water entrapping agent (AO-12) was obtained as a polyorthoester of a colorless transparent oily substance.

The results of ¹ H-NMR measurement of the water entrapment agent (AO-12) were as follows.

_{^{1 H-NMR (CDCl 3)}} ; (2H, q),? 3.44-4.42 (12H, m),? 5.87 (1H, s)

&Lt; Synthesis of water entrapment agent (A3) >

(A3-i), (A3-ii), (A3-ii-2) and (A3-iii) which are examples of the water entrapping agent (A3) contained in the water entrapment forming composition of the embodiment of the present invention. Compounds and (A3-iv) compounds will be described. In the following description, the compounds are respectively referred to as a water capturing agent (A3-i), a water capturing agent (A3-ii), a water capturing agent (A3-ii-2), a water capturing agent It is called capturing agent (A3-iv).

[Synthesis Example 13] Synthesis of water entrapping agent (A3-i)

(0.020 mole) of tetraethoxysilane, 9.628 g (0.083 mole) of 3-ethyl-3-oxetane methanol and 9.628 g (0.083 mole) of 3-ethyl-3-oxetane methanol were placed in a 200 ml three-necked flask equipped with a cooling tube and a stirrer, Aqueous solution and 50 g of tetrahydrofuran as a solvent were placed and stirred. The mixture was stirred at 60 占 폚 for 3 hours. Ethanol and tetrahydrofuran produced by the decompression little by little were distilled off while maintaining the temperature, and water trapping agent (A3-i) was obtained.

The production of the water trapping agent (A3-i) can be carried out by ¹ H-NMR (400 MHz, acetone-d6) in the presence of 3-ethyl-3-oxetane And a peak of? 4.5 to 3.5 derived from a methyloxy group was observed.

[Synthesis Example 14] Synthesis of water entrapping agent (A3-ii)

(0.020 mole) of tetraethoxysilane, 10.80 g (0.083 mole) of 2-hydroxyethyl methacrylate, and a catalytic amount of an aqueous solution of potassium hydroxide (0.08 mole) were added to a 200 ml three-necked flask equipped with a condenser, And 50 g of tetrahydrofuran as a solvent were placed and stirred. The mixture was stirred at 60 占 폚 for 3 hours. Ethanol and tetrahydrofuran produced by reducing pressure little by little was distilled off while maintaining the temperature, and a water entrapping agent (A3-ii) was obtained.

The production of the water trapping agent (A3-ii) can be carried out by ¹ H-NMR (400 MHz, acetone-d6) in the presence of 3-ethyl-3-oxetane And a peak of? 4.5 to 3.5 derived from a methyloxy group was observed.

[Synthesis Example 15] Synthesis of water entrapping agent (A3-ii-2)

(0.020 mol) of tetraethoxysilane and 55 g (0.083 mol) of BLEMMER PP-500 (n = 9, manufactured by Nichiyu) in a dry nitrogen atmosphere, a 200 mL three-necked flask equipped with a cooling tube and a stirrer, Mol), a catalytic amount aqueous solution of potassium hydroxide, and 100 g of tetrahydrofuran as a solvent were placed and stirred. The mixture was stirred at 60 占 폚 for 3 hours. Ethanol and tetrahydrofuran produced by reducing pressure little by little was distilled off while maintaining this temperature, and water trapping agent (A3-ii-2) was obtained.

The production of the water trapping agent (A3-ii-2) can be carried out by ¹ H-NMR (400 MHz, acetone-d6), which is different from the peak of 3-ethyl- And a peak of? 4.5 to 3.5 derived from an oxetane methyloxy group was observed.

[Synthesis Example 16] Synthesis of water entrapping agent (A3-iii)

Under a dry nitrogen atmosphere, to a 200 mL three-necked flask equipped with a cooling tube and a stirrer, 4.64 g (0.020 mol) of 3-methacryloyloxypropylmethyldimethoxysilane and 9.628 g 0.083 mole), a catalytic amount aqueous solution of potassium hydroxide and 100 g of tetrahydrofuran as a solvent were placed and stirred. The mixture was stirred at 60 占 폚 for 3 hours. Methanol and tetrahydrofuran thus produced were distilled off by slightly reducing the pressure while maintaining the temperature, and water trapping agent (A3-iii) was obtained.

The formation of the water trapping agent (A3-iii) can be achieved by ¹ H-NMR (400 MHz, acetone-d6) in the presence of 3-ethyl-3-oxetane And a peak of? 4.5 to 3.5 derived from a methyloxy group was observed.

[Synthesis Example 17] Synthesis of water entrapping agent (A3-iv)

In a 200 mL three-necked flask equipped with a cooling tube and a stirrer, 4.04 g (0.020 mol) of 3-acryloyloxypropyldimethylmethoxysilane and 9.628 g (0.083 mol) of 3-ethyl- Mol), a catalytic amount aqueous solution of potassium hydroxide, and 100 g of tetrahydrofuran as a solvent were placed and stirred. The mixture was stirred at 60 占 폚 for 3 hours. Methanol and tetrahydrofuran produced by distillation under reduced pressure little by little while maintaining this temperature were distilled off to obtain a water entrapping agent (A3-iv).

The formation of the water trapping agent (A3-iv) was confirmed by ¹ H-NMR (400 MHz, acetone-d6) in the presence of 3-ethyl-3-oxetane And a peak of? 4.5 to 3.5 derived from a methyloxy group was observed.

&Lt; Preparation of water entrapment body forming composition >

(A) (the water capturing agent (A1), the water capturing agent (A2), the water capturing agent (A3) and the conventional moisture capturing agent), the component (B) used in preparing the water entrapment forming composition of this embodiment, (D) (radical polymerization initiator (D)) and component (E) (fine particles (E)) are shown below as the component (C) . The AS-1 to AS-6 of the moisture trapping agent (A2) of the component (A) are also shown in terms of their melting points (占 폚).

[Component (A)]

(Water capturing agent (A1))

AO-1: A water-capturing agent (AO-1)

AO-2: Moisture capturing agent (AO-2)

AO-3: Moisture capturing agent (AO-3)

AO-4: Moisture capturing agent (AO-4)

AO-5-1: Moisture capturing agent (AO-5-1)

AO-6: Moisture capturing agent (AO-6)

AO-7: Moisture capturing agent (AO-7)

AO-8: A water-capturing agent (AO-8)

AO-9: Moisture capturing agent (AO-9)

AO-10: A water-capturing agent (AO-10)

AO-11: A water-capturing agent (AO-11)

AO-12: Moisture capturing agent (AO-12)

(Water capturing agent (A2))

AS-1: 4-methylhexahydrophthalic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.) / - 15 ° C

AS-2: 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) / 244 ° C

AS-3: glycerin bisanhydrotrimellitate monoacetate (manufactured by Shin-Etsu Chemical Co., Ltd.) / 65 ° C -85 ° C

AS-4: 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

AS-5: 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (manufactured by Shin-Etsu Chemical Co., Ltd.) / 287 ° C

AS-6: tetrapropenylsuccinic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.) / - 5 ° C

(Water trapping agent (A3))

A-1: Moisture capturing agent (A3-i)

A-2: Moisture capturing agent (A3-ii)

A-3: Water entrapment agent (A3-ii-2)

A-4: Water trapping agent (A3-iii)

A-5: Moisture capturing agent (A3-iv)

(Conventional moisture capturing agent)

AX-1: Aluminum triisopropoxide (Al (i-PrO) ₃ ) (manufactured by Tokyo Chemical Industry Co., Ltd.)

AX-2: Calcium oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Component (B)]

B-1: CPI-200K (manufactured by San A &

B-2: Sun Aid (registered trademark) SI-80L (manufactured by Sanxin Chemical Co., Ltd.)

B-3: 2-Nitrophenylmethyl-4-methacryloyloxypyridine-1-carboxylate

[Component (C)]

C-1: Epikote (registered trademark) 828 (manufactured by Mitsubishi Chemical Corporation)

C-2: Denacol (registered trademark) EX-212 (manufactured by Nagase)

C-3: NK ester 9PG (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Component (D)]

D-1: Lucirin (registered trademark) TPO (manufactured by BASF)

D-2: V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)

[Component (E)]

E-1: Nano-use (registered trademark) OZ-S30K-AC (primary particle diameter 20 nm, average particle size by dynamic light scattering of zirconium oxide, solid concentration 20 mass%) manufactured by Nissan Chemical Industries,

E-2: RTTCHN15WT% -E06 (primary particle size of titanium oxide: 25 nm, average particle diameter by dynamic light scattering: 100 nm, solid content concentration: 15 mass%),

[Example 1] (Preparation of water entrapment body forming composition (JO-1)) [

20 parts by mass of (AO-1) which is the water trapping agent (A1) of the component (A) was added to 80 parts by mass of the component (C-1) under an atmospheric environment to prepare a homogeneous solution, , 1 part by mass of (B-1) as the component (B) was added to prepare a water entrapment body forming composition (JO-1). The components and blending amounts used are summarized in Table 1 together with other examples to be described later.

[Examples 2 to 19 and Comparative Examples 1 to 4]

(Preparation of moisture entrapment forming compositions (JO-2) to (JO-23)) [

A composition for forming each water entrapment body was prepared in the same manner as in Example 1 except that each component of the type and compounding amount shown in Table 1 below was used.

In Examples 17 to 19, the amount of the component (E) corresponding to the solid content shown in Table 1 was used.

[Example 20] (Preparation of water entrapment body forming composition (JS-1)) [

20 parts by mass of (AS-1) which is the water trapping agent (A2) of the component (A) was added to 80 parts by mass of the component (C-1) under an atmospheric environment to prepare a homogeneous solution, , 1 part by mass of (B-1) as the component (B) was added to prepare a water entrapment body forming composition (JS-1). The components and blending amounts used are summarized in Table 2 together with other examples to be described later.

[Examples 21 to 32 and Comparative Example 5]

(Preparation of moisture entrapment forming compositions (JS-2) to (JS-14)

A composition for forming each water entrapment body was prepared in the same manner as in Example 20 except that each component of the type and compounding amount shown in Table 2 below was used.

In Examples 30 to 32, the component (E) was used in an amount corresponding to the solid content shown in Table 2.

[Example 33] (Preparation of water entrapment body forming composition (J-1)) [

20 parts by mass of (A-1) as the water trapping agent (A3) of the component (A) was added to 80 parts by mass of the component (C-1) as the component (C) under an atmospheric environment to prepare a homogeneous solution, , 1 part by mass of (B-1) as the component (B) was added to prepare a water entrapment body forming composition (J-1). The components and blending amounts used are summarized in Table 3 together with other examples to be described later.

[Examples 34 to 44 and Comparative Example 6] (Preparation of water entrapment body forming composition (J-2) to (J-13)) [

A composition for forming each water entrapment body was prepared in the same manner as in Example 33 except that each component of the type and compounding amount shown in the following Table 3 was used.

In Examples 40 to 44, the component (E) was used in an amount corresponding to the solid content shown in Table 3.

&Lt; Production of organic EL device >

On a glass substrate (manufactured by Asahi Glass Co., Ltd.) having an ITO film with a thickness of 15 nm and a thickness of 2 mm formed on a glass plate having a length of 25 mm and a thickness of 0.7 mm, poly (3,4) A hole injection layer formation liquid containing an opene / polystyrene sulfonate (PEDOT / PSS) was spin-coated at 3000 rpm for 50 seconds to form a hole injection layer having a thickness of 50 nm. Then, Followed by heating and drying for a minute. Here, PEDOT / PSS dissolved in pure water at a solid content of 0.1% by mass was used as a coating liquid for forming the hole injection layer. A 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated on the hole injection layer at 2000 rpm for 50 seconds to form an organic light emitting layer having a thickness of 70 nm, followed by baking at 60 캜 for 10 minutes. LiF was deposited at a deposition rate of 0.1 nm / sec under a pressure of 10 ^-5 Pa on the organic light-emitting layer, and Ca was deposited to a thickness of 20 nm at a deposition rate of 0.1 nm / sec. Al was laminated at a rate of 100 nm to form a cathode.

Subsequently, each of the moisture trapping forming compositions described above was applied by spin coating onto the organic EL layer formed on the glass substrate, and a coating film having a thickness of 50 탆 was formed by heating at 120 캜 for 5 minutes. The film thickness of the coating film was measured by Depth gauges 547-251 (manufactured by Mitsutoyo Co., Ltd.). Subsequently, a composition having the same composition as that of the moisture trapping-forming composition obtained in Comparative Example 1 was applied to the periphery of the obtained glass substrate with the use of a dispenser to form a coating film having a thickness of 100 탆.

Subsequently, an opposing glass substrate having a thickness of 25 mm and a thickness of 0.7 mm was adhered to the glass substrate on which the film had been formed, using the vacuum bonding apparatus, through the above-mentioned coating film, and as a condition of water entrapment (curing) (UV intensity) of 1 J / cm &lt; 2 &gt;, and then heated at 80 DEG C for 30 minutes to cure the coating film to form a water entrapment body and a sealant. Example 3, Example 5, Example 22, Example 24, and Example 36 By using a vacuum bonding apparatus, an opposing glass substrate having a film thickness of 25 mm and a thickness of 0.7 mm was laminated on a glass substrate having the film formed thereon, , Heated at 100 占 폚 for 30 minutes and then heated at 80 占 폚 for 30 minutes to cure the coating film to form a water entrapment body and a sealant.

Thus, an organic EL device was manufactured.

<Evaluation>

Film formability, heat resistance, glass adhesion, light-emitting appearance, and light extraction efficiency of each of the moisture trapping body forming compositions of Examples 1 to 44 and Comparative Examples 1 to 6 prepared above were evaluated according to the following methods. The evaluation results are shown in Tables 1, 2 and 3.

[Formability]

Using each of the prepared water entrapment forming compositions prepared above, a glass substrate having a long side of 66 mm, a short side of 24 mm and a thickness of 1.1 mm was formed into a bodyshaped with a long side of 58 mm, a short side of 13 mm and a depth of 0.3 mm, Forming composition was applied and then cured by UV irradiation (irradiation energy: 1 J / cm 2) using a high-pressure mercury lamp to form a water entrapment body, and visual observation was performed by visual observation. At this time, when cracks and irregularities were not confirmed, film forming property was evaluated as good &quot;? &Quot;. When at least one of cracks and irregularities was confirmed,

[Heat resistance]

In the sample tube, each of the prepared water entrapment forming compositions was added in an appropriate amount, and a water entrapment body having a film thickness of 2 mm was formed at the bottom of the sample tube under the same conditions as the curing conditions of the aforementioned [film formability]. Subsequently, the formed water entrapment body was exposed to the atmosphere to sufficiently absorb moisture, and then the lid of the sample tube was closed and sealed, and the sample was allowed to stand under an environment of 85 DEG C in a state where the bottom of the sample tube was fixed so as to be above the film surface. Thereafter, the state of the water entrapment state was observed at a point of 336 hours. In this case, when the change in the water entrapment body was not completely confirmed, the heat resistance was evaluated as &quot; good &quot;. When only a very slight change was confirmed, the water entrapment body was evaluated as good & When it was confirmed, it was evaluated as defective &quot; x &quot;.

[Glass adhesion property]

Using each of the prepared moisture entrapment forming compositions, a glass substrate having a long side of 66 mm, a short side of 24 mm and a thickness of 1.1 mm was immersed in a water entrapment body having a film thickness of 2 mm . The presence or absence of peeling of each moisture trapping body from the glass substrate in the air was observed. At this time, when the peeling was not confirmed, the adhesion was evaluated as good &quot;? &Quot;

(Evaluation of organic EL device) (Evaluation of luminous appearance (dark spot, unevenness), light extraction efficiency)

For each of the organic EL devices obtained in the above-mentioned [Production of organic EL device], a forward current at 10 mA / cm 2 was passed at room temperature to observe a light-emitting appearance (dark spot, unevenness). Further, the front luminance was measured by a spectroscopic radiation luminance meter &quot; CS-2000 &quot; manufactured by Konica Minolta Sensing Co., Ltd., and the front luminance of the organic EL device fabricated on the substrate on which the light scattering layer was not formed was measured, The improvement rate of the front luminance of the light emitting element was calculated.

Evaluation was made based on the following criteria.

· Luminous appearance (dark spot, unevenness)

Dark spot, no unevenness observed: Good (O), Good

Dark spot, unevenness observed: bad (x)

· Efficiency of light extraction

Front luminance improvement rate 1.2 times or more: excellent (⊚),

Front luminance improvement rate 1.0 times or more to 1.2 times or less: Good (O),

Front luminance improvement rate less than 1.0 times: bad (x)

As is evident from the evaluation results of Tables 1 to 3, the water entrapment body formed of the water entrapment body forming composition of this example and the water entrapment body forming composition of this example exhibited good or very good film forming properties, heat resistance, It was good. On the other hand, in the water entrapment body formed of the composition for forming a water entrapment body according to the comparative example, the heat resistance was poor.

The present invention can provide a water entrapment body forming composition capable of handling under air and capable of forming a water entrapment body which is hard to cause volatile decomposition products. Therefore, the present invention can provide a water entrapment body formed of the moisture entrapment body forming composition and an electronic device having the water entrapment body with high productivity. In particular, it can be suitably used for electronic devices such as organic EL devices for suppressing occurrence of dark spots and liquid crystal display devices for suppressing the influence of moisture.

10: organic EL layer
20: Structure
22: substrate
24: sealing substrate
26: Seal material
30, 130: Water entrapment body
40: Gas barrier film
100, 200, 300, 400, 500: Organic EL device

Claims (5)

An organic EL device having a moisture trapping body,
Wherein the water-
(A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound,
(B) at least one compound selected from the group consisting of an acid generator and a base generator,
(C) a curable compound. The method according to claim 1,
The compound (A)
(A1) at least one compound selected from a compound represented by the formula (A1-1), a compound represented by the formula (A1-2) and a compound represented by the formula (A1-3)
(A2) at least one compound selected from a carbonic anhydride and a carbonic acid compound, and
(A3) at least one compound selected from the group consisting of a compound represented by the formula (A3-1), a compound represented by the formula (A3-2) and a compound represented by the formula (A3-3) &Lt; / RTI &
An organic EL device characterized in that the compound (B) is an acid generator:

Wherein R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or a group having 1 to 18 carbon atoms R ³ , R ⁴ and R ⁷ may be combined with a carbon atom to which they are directly bonded to form a cyclic structure, n is 0 or an integer of 1 to 18, * represents a bonding position ;
In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms;
R ⁸ is each independently an organic group having 3 to 30 carbon atoms;
In the formula (A1-3), the formula R ⁸ is the same as the formula (A1-2);

[In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom;
R ²¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group;
R ²² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxirane group, a 3,4-epoxycyclohexyl group, or a mercapto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30; The method according to claim 1,
The compound (A)
(A2) at least one compound selected from a carbonic anhydride and a carbonic acid compound, and
(A3) at least one compound selected from the group consisting of a compound represented by the formula (A3-1), a compound represented by the formula (A3-2) and a compound represented by the formula (A3-3) &Lt; / RTI &
An organic EL device wherein the compound (B) is a base generator:

[In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom;
R ²¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group;
R ²² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxirane group, a 3,4-epoxycyclohexyl group, or a mercapto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30; 4. The method according to any one of claims 1 to 3,
Wherein said moisture trapping body further comprises (D) a radical polymerization initiator. 6. The method according to any one of claims 1 to 5,
Wherein the moisture trapping body further contains (E) fine particles.

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