JP2015027665A - Composition for formation of moisture capture body, moisture capture body and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for formation of a moisture capture body for forming a moisture capture body allowing handling in air, a moisture capture body and an electronic device.SOLUTION: A composition for formation of a moisture capture body comprises (A) at least one compound selected from siloxane compounds, titanium compounds and zirconium compounds and (B) at least one of acid-generating agents and base-generating agents. An organic EL element 100, an electronic device, is produced by forming a moisture capture body 30 by using the composition for formation of a moisture capture body and sealing the moisture capture body, together with an organic EL layer 10, in a structure 20.

Description

  The present invention relates to a moisture trap forming composition, a moisture trap and an electronic device.

  As one of electronic devices that have been actively developed in recent years, for example, organic electroluminescence (EL) elements are known. The organic EL element is a simple device having a basic structure of a laminated structure composed of an anode / organic light emitting layer / cathode, but has a problem that the organic light emitting layer is easily affected by moisture.

  That is, in the organic EL element, as the driving period becomes longer, there is a concern that so-called dark spots may be formed due to the influence of moisture that has entered the element, and light emission characteristics such as luminance and light emission efficiency may be gradually decreased. have. Therefore, the organic EL element needs to be used in a state where moisture in the element is removed and sealed, but it is difficult to completely seal such an electronic device by sealing.

  Then, the organic EL element which arrange | positions the moisture capture agent which consists of a specific organometallic compound beforehand in an electronic device, and keeps the inside of an electronic device in a low-humidity environment by making this moisture capture agent capture a water | moisture content is proposed ( For example, see Patent Document 1.)

Japanese Patent No. 3936151

  However, for example, the organoaluminum compounds exemplified as the moisture trapping agent in Patent Document 1 and the like are very reactive and there is a concern that they react with moisture in the air. Therefore, handling in air is difficult, and when using a conventional moisture scavenger, handling under air or nitrogen controlled to a sufficiently low humidity has been essential. Therefore, when an electronic device is manufactured using a conventional moisture trapping agent, the manufacturing process is complicated, for example, an operation in a low humidity atmosphere is required.

  Therefore, there is a need for a moisture trap forming composition that can be handled under normal air and can be used in the manufacture of electronic devices such as organic EL elements and liquid crystal display elements.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to capture moisture that can be handled under air in an electronic device such as an organic EL element and a liquid crystal display element, while removing moisture in the element and reducing moisture intrusion into the element. The object is to provide a composition for forming a moisture trap that forms a body. Another object of the present invention is to provide an electronic device having a moisture trap formed from the above-mentioned composition for forming a moisture trap.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by a composition for forming a moisture trap having the following configuration, and the present invention has been completed.

  For example, the present invention relates to the following [1] to [7].

[1] (A) at least one compound selected from the group consisting of a siloxane compound, a titanium compound and a zirconium compound;
(B) It relates to a composition for forming a moisture trap, comprising at least one compound selected from the group consisting of an acid generator and a base generator.

  [2] The compound (A) is at least one selected from the group consisting of a compound represented by the formula (A1-1) and a compound represented by the formula (A1-2). [1] The composition for forming a moisture trap.

［式（Ａ１−１）および（Ａ１−２）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ^１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４−エポキシシクロヘキシル基、メルカプト基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１〜６のアルキル基、炭素数３〜１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ^２は、水素原子、置換基を有してもよい炭素数１〜２０のアルキル基、置換基を有してもよい炭素数３〜１２のシクロアルキル基、置換基を有してもよい炭素数６〜１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４−エポキシシクロヘキシル基、またはメルカプト基であり；
ｐは０〜６の整数であり；
ｒは０〜２の整数であり、ｓは１〜３０の整数である。］

[In the formulas (A1-1) and (A1-2), X is a silicon atom, a titanium atom or a zirconium atom; R ¹ is a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, or a 3,4-epoxy. An organic group having at least one group selected from a cyclohexyl group, a mercapto 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 ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon. Aromatic hydrocarbon group of formulas 6 to 14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or It is 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 composition for forming a water trap according to [1] or [2], further comprising a curable compound.

  [4] The composition for forming a moisture trap according to any one of [1] to [3], further comprising a radical polymerization initiator.

  [5] The composition for forming a moisture trap according to any one of [1] to [4], further comprising fine particles.

  [6] A moisture trap formed from the composition for forming a moisture trap according to any one of [1] to [5].

  [7] An electronic device comprising the moisture trap according to [6].

  According to the present invention, in an electronic device such as an organic EL element and a liquid crystal display element, a moisture trap body that removes moisture in the element, reduces moisture intrusion into the element, and can be handled under air. A composition for forming a moisture trap can be provided. For this reason, the moisture trap obtained from the composition for forming a moisture trap of the present invention has an organic EL element such as an organic EL illumination or an organic EL display element that can suppress the generation of dark spots even when driven for a long time, It can be suitably used as a constituent element of a liquid crystal display element included in TVs, portable information devices, and the like that require high reliability.

It is sectional drawing which shows typically the 1st example of the organic EL element of embodiment of this invention. It is sectional drawing which shows typically the 2nd example of the organic EL element of embodiment of this invention. It is sectional drawing which shows typically the 3rd example of the organic EL element of embodiment of this invention. It is sectional drawing which shows typically the 4th example of the organic EL element of embodiment of this invention. It is sectional drawing which shows typically the 5th example of the organic EL element of embodiment of this invention.

  An electronic device such as a composition for forming a moisture trap of the present invention, a moisture trap formed using the composition, and an organic EL element having the moisture trap will be described.

<Composition for moisture trap formation>
The composition for forming a moisture trap of the embodiment of the present invention is (A) at least one compound selected from the group consisting of a siloxane compound, a titanium compound and a zirconium compound (hereinafter simply referred to as (A) compound, And (B) component), and (B) at least one compound selected from the group consisting of an acid generator and a base generator (hereinafter referred to simply as (B) compound, and (B) Also referred to as an ingredient). The composition may further contain (C) a curable compound (hereinafter, simply referred to as (C) curable compound, and sometimes referred to as (C) component).

  Hereinafter, each component will be described in detail.

[(A) Compound]
The composition for forming a moisture trap of the embodiment of the present invention is selected from the group consisting of a compound represented by the following formula (A1-1) and a compound represented by the formula (A1-2) as the component (A). It contains at least one kind.

  In the above formulas (A1-1) and (A1-2), X represents a silicon atom, a titanium atom, or a zirconium atom. Among these, a silicon atom is preferable.

In the above formulas (A1-1) and (A1-2), R ¹ is at least one selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, and an isocyanate group. An organic group having the above 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.

In the above formulas (A1-1) and (A1-2), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 3 carbon atoms that may have a substituent. -12 cycloalkyl group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group Or a mercapto group.

  In said formula (A1-1) and (A1-2), p shows the integer of 0-6.

  In said formula (A1-1) and (A1-2), r shows the integer of 0-2 and s shows the integer of 1-30.

In the compound represented by the above formula (A1-1) of the component (A) and the compound represented by the above formula (A1-2), examples of the organic group include groups represented by the following formulas. . In the following formula, * represents a bond position, R ³ is a hydrogen atom or a methyl group, R ⁴ is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 3.

In addition, the alkyl group in R ¹ in the above formula (A1-1) and the above formula (A1-2) may be linear or branched. For example, methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, t-butyl, pentyl, hexyl can be mentioned, and examples of the cycloalkyl group include cyclohexyl.

In the compound represented by the above formula (A1-1) of the component (A) and the compound represented by the above formula (A1-2), the alkyl group in R ² may be any of linear, branched and cyclic Good. Although the number of carbon atoms in the alkyl group in R ² is 1 to 20, carbon atoms 1 to 10 preferably 1 to 6 is more preferable. Specifically, in addition to the alkyl group exemplified for R ¹ , n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, cycloheptyl group, cyclooctyl group and the like.

Examples of the aromatic hydrocarbon group for R ² in the above formula (A1-1) and the above formula (A1-2) include monocyclic to tricyclic aromatic hydrocarbon groups. Include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferable, and a phenyl group is more preferable.

Furthermore, the alkyl group, cycloalkyl group and aromatic hydrocarbon group in R ² in the above formula (A1-1) and the above formula (A1-2) may have a substituent. Examples thereof include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. In addition, the position and number of substituents are arbitrary, and when it has two or more substituents, 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 these, a fluorine atom is preferable. The halogen atom can substitute a part or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aromatic hydrocarbon group, but preferably all are substituted. Specific examples of the halogen-substituted alkyl group and the halogen-substituted cycloalkyl group include perfluoroalkyl groups such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorocyclopropyl group, and perfluoroalkyl groups. A cycloalkyl group is mentioned. Moreover, as a C1-C6 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, and iso-propoxy group are mentioned, for example.

The (meth) acryloyloxy group in R ² described above is a concept including an acryloyloxy group and a methacryloyloxy group.

Among those exemplified above, R ² is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a (meth) acryloyloxy group. In addition, when ^two or more R2 exists in the same molecule, they may be the same or different.

  In the compound represented by the above formula (A1-1) of the component (A) and the compound represented by the above formula (A1-2), p is an integer of 0 to 6, preferably an integer of 0 to 3. 0 or 3 is more preferable.

  In the compound represented by the above formula (A1-1) and the compound represented by the above formula (A1-2) of the component (A), s is an integer of 1 to 30, but an integer of 1 to 20 Is preferable, and an integer of 1 to 10 is more preferable.

  More specific examples of the compound represented by formula (A1-1) of the component (A) and the compound represented by formula (A1-2) include a silane compound in which X is a silicon atom. Can do.

  In the compound represented by the formula (A1-1), examples of the silane compound in which r is 0 and s is 1 include two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane. Alkoxysilane compound having two C6-C14 aromatic hydrocarbon groups such as diphenyldimethoxysilane; 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyl (Meth) acryloyloxy such as oxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane Alkoxysilane compound having a group and an alkyl group having 1 to 20 carbon atoms; 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldiethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropyl An alkoxysilane compound having a (meth) acryloyloxy group such as phenyldiethoxysilane and an aromatic hydrocarbon group having 6 to 14 carbon atoms; 3,3′-dimethacryloyloxypropyldimethoxysilane, 3,3′-diacryloyl Alkoxysilane compounds having two (meth) acryloyloxy groups such as oxypropyldimethoxysilane; 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane An alkoxysilane compound having a glycidoxy group and an alkyl group having 1 to 20 carbon atoms, such as 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropylethyldiethoxysilane; 3-glycidoxypropylphenyldimethoxysilane And alkoxysilane compounds having a glycidoxy group such as 3-glycidoxypropylphenyldiethoxysilane and an aromatic hydrocarbon group having 6 to 14 carbon atoms.

  In the compound represented by the formula (A1-1), examples of the silane compound in which r is 1 and s is 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, and methyltributoxy. Alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-iso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane An alkoxysilane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane; an aromatic hydrocarbon group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane; Al with one Xylsilane compound; 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3- Examples include alkoxysilane compounds having one (meth) acryloyloxy group such as acryloyloxypropyltripropoxysilane.

  In the compound represented by the formula (A1-1), examples of the silane compound in which r is 2 and s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxy. Examples include silane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane.

  Examples of the compound represented by the formula (A1-1) further include compounds represented by the following formula (A1-i), formula (A1-ii), and formula (A1-ii-2). The compound of the formula (A1-i), the formula (A1-ii) and the formula (A1-ii-2) has a hydroxyl group and a polymerizable group (oxiranyl group, It can be obtained by reacting a compound having both an oxetanyl group and a (meth) acryloyl group in the presence of an alkali.

  Examples of the compound represented by the formula (A1-1) include compounds represented by the following formulas (A1-iii) and (A1-iv). The compounds of formula (A1-iii) and formula (A1-iv), as shown by the following formula, are converted to a silane compound having a methoxy group with a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl). Group) and the like, can be obtained by reacting in the presence of an alkali.

  Examples of the compound represented by the formula (A1-1) further include a compound represented by the following formula (A1-v).

Moreover, as a compound represented by the said Formula (A1-2),
3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldiethylethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropyldiethylmethoxysilane, 3-acryloyloxypropyl An alkoxysilane compound having one (meth) acryloyloxy group such as dimethylethoxysilane and two alkyl groups having 1 to 20 carbon atoms;
It has one (meth) acryloyloxy group such as 3-methacryloyloxypropyldiphenylmethoxysilane, 3-methacryloyloxypropyldiphenylethoxysilane, 3-acryloyloxypropyldiphenylmethoxysilane, 3-acryloyloxypropyldiphenylethoxysilane, and carbon. An alkoxysilane compound having two aromatic hydrocarbon groups of formula 6-14;
It has one glycidoxy group such as 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and two alkyl groups having 1 to 20 carbon atoms. Having an alkoxysilane compound;
Examples thereof include silane compounds having one glycidoxy group such as 3-glycidoxypropyldiphenylmethoxysilane and 3-glycidoxypropyldiphenylethoxysilane and two aromatic hydrocarbon groups having 6 to 14 carbon atoms.

  In the compound represented by the above formula (A1-1) of the component (A) and the compound represented by the above formula (A1-2), as a commercially available product, for example, OXT-191 (manufactured by Toagosei Co., Ltd.) ) And X-22-3000T (manufactured by Shin-Etsu Chemical Co., Ltd.).

<Description of effects>
The effects of the composition for forming a moisture trap according to the embodiment of the present invention will be described below.

  The composition for forming a water trap according to an embodiment of the present invention is at least one compound selected from the group consisting of (B) an acid generator and a base generator when heated and / or irradiated with light ( B) Acid or base is formed from component. Based on the water present in the system in which the composition is used, the acid or base promotes the hydrolysis reaction of component (A), thereby consuming water present in the system with high efficiency. Can do. In the present specification, “moisture capture” is used in this sense. The hydrolysis product of the component (A) is less likely to deteriorate the performance of electronic devices such as organic EL elements and liquid crystal display elements as will be described later.

  For this reason, in this invention, when forming the moisture trap of the said electronic device using the said composition for water trap formation, the water | moisture content in an element can be removed with high efficiency. In addition, in the moisture trap such as a sealing material formed from the composition for forming a moisture trap according to the embodiment of the present invention, the component (A) or a part of the structure derived therefrom remains partially without being decomposed. it seems to do. For this reason, the moisture in the element can be absorbed for a long period of time after the formation, and the deterioration of the characteristics of the electronic device due to the moisture can be suppressed.

  In general, the decomposition products are dispersed in the organic EL element by volatilization or the like, reach the organic EL layer that becomes the light emitting layer of the organic EL element, contaminate, and generate dark spots. There is a concern of degrading the performance of the EL element. However, in the present invention, since the hydrolysis product produced from the component (A) has an appropriate molecular weight, volatilization and the like are suppressed, and can remain in a moisture trap such as a sealing material. . As the hydrolyzed product has a larger molecular size, it tends to stay in the moisture trap, and therefore, the component (A) is preferably a compound having a relatively large molecular weight.

  The component (A) used in the embodiment of the present invention hardly generates a highly volatile hydrolysis product such as a low-molecular alcohol even when moisture is captured, for example, Even when it is used in an organic EL element that easily generates dark spots due to adhesion, the generation of dark spots due to adhesion of the decomposition products to the organic EL layer can be suppressed. And after the moisture trap of the embodiment of the present invention is formed, the (A) component of the composition for forming a moisture trap or a part of the structure derived therefrom remains partially undecomposed. Therefore, the moisture trap of the embodiment of the present invention can be used for a long period of time by using the component (A) of the composition for forming a moisture trap or a structural portion derived therefrom, such as in an organic EL element. It is possible to consume water in the system in which it is placed.

  Examples of the hydrolysis reaction of the compound (A) used in the embodiment of the present invention are shown below.

  About the effect of the composition for moisture trap formation of embodiment of this invention, for example, the following chemical reaction formula is used using the compound represented by the said Formula (A1-2) which is an example of (A) component. More specifically.

  In addition, the composition for forming a moisture trap of the embodiment of the present invention, for example, when the compound of the above formula (A1-2) is hydrolyzed according to the above chemical reaction formula, the alcohol compound (3) and the metal are decomposed as decomposition products. An alkoxide compound (4) is produced. When the composition for forming a moisture trap of the embodiment of the present invention is applied, for example, to the manufacture of an organic EL device, the alcohol compound (3) and the metal alkoxide compound (4) generated by trapping moisture are, for example, , Volatilization, etc., and may be dispersed in the organic EL element. In such a case, the alcohol compound (3) and the metal alkoxide compound (4) reach the organic EL layer that becomes the light emitting layer of the organic EL element and are contaminated to generate dark spots. There is.

However, the alcohol compound (3) produced from the component (A) of the moisture trap forming composition of the present embodiment reacts using the above R ¹ group, and the moisture trap forming composition to be described later. It can remain in the moisture trap that is formed. Since the alcohol compound (3) to be produced tends to stay in the moisture trap as the molecular size increases, a compound having a relatively large molecular weight is desirable.

Similarly, the metal alkoxide compound generated from the component (A) of the moisture trap body composition of the present embodiment (4) is reacted with R ² groups described above, formed from a moisture trap body composition Can stay in the moisture trap. Furthermore, the metal alkoxide compound (4) is fixedly held in the moisture trap by the R ² group and scattered in the moisture trap, thereby preventing the re-generation of water due to the condensation reaction.

[(B) Acid generator and base generator]
In the composition for forming a water trap according to an embodiment of the present invention, an acid generator (hereinafter also referred to as an acid generator (B1)) and a base generator (hereinafter referred to as a base generator (B2)) are used as the component (B). It is also configured to contain at least one compound selected from the group consisting of:

Examples of the acid generator (B1) include a radiation sensitive acid generator and a thermal acid generator, and a radiation sensitive acid generator is preferable. 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.
A radiation-sensitive acid generator and a radiation-sensitive base generator can be defined as compounds capable of releasing an acidic active substance and a basic active substance, respectively, by irradiating them with radiation.

  A radiation-sensitive acid generator that is preferably used as the component (B) of the composition for forming a water trap according to the present embodiment, or a feeling that is preferably used as the component (B) of the composition for forming a water trap according to the present embodiment. The radioactive base generator hydrolyzes the compound represented by the above formula (A1-1) and the compound represented by the above formula (A1-2), which are the above component (A), by irradiating with radiation. Acts as a catalyst for the reaction.

  The radiation irradiated to decompose the radiation-sensitive acid generator or the radiation-sensitive base generator, which is the component (B), to generate the cation of the acidic active substance or the anion of the basic active substance is described above. As described above, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like can be given. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.

  In the composition for forming a moisture trap according to the embodiment of the present invention, the content when the component (B) is the acid generator (B1) is preferably 0.00 with respect to 100 parts by mass of the component (A). It is 001 mass part-20 mass parts, More preferably, it is 0.01 mass part-10 mass parts. By setting the content of the component (B) within the above range, for example, a composition for forming a moisture trap with excellent radiation sensitivity can be obtained.

  In the composition for forming a water trap according to the embodiment of the present invention, the content when the component (B) is the base generator (B2) is preferably 0.00 with respect to 100 parts by mass of the component (A). It is 001 mass part-20 mass parts, More preferably, it is 0.01 mass part-10 mass parts. By setting the content of the component (B) within the above range, for example, a composition having excellent radiation sensitivity can be obtained.

  In the composition for forming a moisture trap according to 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, light or thermal cation curing catalysts such as iodonium salts, sulfonium salts, phosphonium salts, and anion curing catalysts such as imidazoles and acid anhydrides can be used. In these, a cationic curing catalyst is preferable and a photocationic curing catalyst is more preferable. This is because the curing rate is high and the polymerization reaction does not start unless light is applied, so that the storage stability is good.

Specific examples of the cation curing catalyst include cations such as iodonium, sulfonium, and phosphonium substituted with an alkyl group or an aryl group, SbF ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , and PF _{6. ^{-, P (Rf) n F}} (6-n) - (Rf is, for example, perfluoroalkyl group having 1 to 8 carbon atoms; n is an integer of 1 to _{3), C n F 2n + 1} SO 3 - (n is , for example, an integer of 1 to ^{_{8), N (SO 2 CF 3}} ) 2 -, C (SO 2 CF 3) 3 - anions consisting of salts and the like are used. Specifically, CPI-100P, CPI101A, CPI-200K, CPI-210S and the like (manufactured by Sun Apro), SunAid (registered trademark) SI-150L, SunAid (registered trademark) SI-110L, SunAid (registered trademark) SI CI series such as -60L, Sun Aid (registered trademark) SI-80L, Sun Aid (registered trademark) SI-100L, etc. (manufactured by Sanshin Chemical Industry), Rhodia PI-2074, Nippon Soda CI2920, etc., ADEKA Optomer ( Optomer (registered trademark) SP series such as (registered trademark) SP-150, Opton CP series (such as CP-66), WPA series manufactured by Wako Pure Chemical Industries, and WPI series.

Of these acid generators (B1), in cationic curing catalyst, _B from the viewpoint of reactivity as the anion ^{_{(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 preferred, and the cation is preferably a sulfonium cation substituted with an alkyl group or an aryl group from the viewpoint of storage stability.

<Base generator (B2)>
The base generator (B2) is preferably a radiation-sensitive base generator, and the radiation-sensitive base generator is not particularly limited as long as it is a compound that generates a base such as an amine upon irradiation with radiation. Examples of the radiation sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, acyloxyiminos, and α, α-dimethyl-3,5-dimethoxybenzyl carbamates.

  Transition metal complexes include, for example, bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) oxy Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [ (2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate.

  Acyloxyiminos include, for example, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime may be mentioned.

  Other examples of radiation sensitive base generators include bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate and acrolate. Ilbenzophenone oxime is particularly preferred.

[(C) curable compound]
(C) The curable compound is a compound having a polymerizable group. Crosslinking reactivity can be improved because the composition for moisture trap formation of embodiment of this invention contains the (C) curable monomer. And the film | membrane intensity | strength of the moisture capture body of embodiment of this invention formed from this composition for moisture capture body formation and adhesiveness with a board | substrate can be improved. In addition, (C) a curable compound can be used individually or in combination of 2 or more types.

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

  Examples of the 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 a monofunctional epoxy compound,
Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p- Ethyl phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl, etc.
As a multifunctional epoxy compound,
Polyglycidyl ethers of bisphenols such as 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 diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ethers;
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;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3 , 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3, 4-D Carboxymethyl epoxycyclohexylmethyl-3 ', compounds having a 4'-epoxycyclohexane carboxylate of the 3,4-epoxycyclohexyl group.

As a compound having the above oxetanyl group, for example,
As monofunctional oxetane compounds,
3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dodecyloxymethyl) oxetane, 3 -Ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, etc.
As a polyfunctional oxetane compound,
Xylylenebisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl } Oxetane, 1,1,1-tris [(3-ethyloxetane-3-yl) methoxymethyl] propane and the like.

  Among these, the compound having a cyclic ether group is preferably a compound having an epoxy group, more preferably a polyfunctional epoxy compound, and more preferably polyglycidyl ethers of polyhydric alcohols from the viewpoint of enhancing the crosslinking reactivity. Polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are particularly preferable.

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

  As said (meth) acrylate compound, a monofunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound, etc. are mentioned, for example.

  Examples of the monofunctional (meth) acrylate compound include (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, tetrahydrofurfuryl ( Acrylate), tetrabromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) Acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, isobornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy 2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl ( ) Acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, and ethylene oxide reacted Milphenol (meth) acrylate, 2-bromophenoxyethyl (meth) acrylate, 4-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,6-dibromophenoxyethyl (meth) Examples thereof include acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, and the like.

  Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecanediyl. Dimethylene di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate , PO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate , Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditri Methylolpropane tetra (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, 1,3-bis ((meth) acryloyloxy) -2-propanol, 9,9-bis [4- [2- (acryloyloxy) ) Ethoxy] phenyl] -9H-fluorene and the like. Among these, polypropylene glycol di (meth) acrylate is preferable as the polyfunctional (meth) acrylate compound.

  As a commercial item of the above-mentioned polyfunctional (meth) acrylate compound, for example, biscoat # 195, # 230, same # 260, same # 335HP, same # 540, same # 700 (above, manufactured by Osaka Organic Chemical Industry), Examples include TMPT, 9G, 9PG, 701, BPE-500, DCP, DOD-N, HD-N, NOD-N, NPG (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

  Among these, the compound having a polymerizable double bond is preferably a polyfunctional (meth) acrylate compound, more preferably a polyfunctional methacrylate compound, polyethylene glycol dimethacrylate, polypropylene from the viewpoint of enhancing the crosslinking reactivity. Glycol dimethacrylate is more preferred, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferred.

  (C) As content of a sclerosing | hardenable compound, 10 mass parts-3000 mass parts are preferable with respect to 100 mass parts of (A) component, and 50 mass parts-2000 mass parts are more preferable. (C) By making content of a sclerosing | hardenable compound into the said range, it is effective from the adhesiveness to the board | substrate of the moisture capture body of embodiment of this invention formed from the composition for moisture capture body formation of this embodiment. Can be enhanced.

[Other optional ingredients]
The composition for forming a moisture trap of the embodiment of the present invention is at least selected from (D) a radical polymerization initiator, (E) fine particles, and an additive as long as the effects of the present invention are not impaired. One other component may be contained. Other components may be used alone or in combination of two or more.

[(D) Radical polymerization initiator]
The composition for forming a moisture trap of the embodiment of the present invention may further contain (D) a radical polymerization initiator. (D) The radical polymerization initiator means a compound that generates radicals with actinic rays, heat, acid, or base, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator. (D) By containing the radical polymerization initiator, for example, the alcohol compound and the metal alkoxide compound formed by the hydrolysis reaction shown in the above chemical reaction formula are efficiently contained in the moisture trap formed from the composition. It is well fixed and easy to stay.

  In the composition for forming a water trap according to the embodiment of the present invention, the (D) radical polymerization initiator may be used alone or in combination of two or more.

  Examples of the thermal radical polymerization initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl- 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′- Azobis [N- (2-propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide) Azo compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide); t-butylperoxybenzoate, 2,5-dimethyl-2,5- Peroxides such as (t-butylperoxy) hexane and the like. Among these, as the thermal radical polymerization initiator, an azo compound is preferable, and dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (N-butyl-2-methylpropion). Amide) and 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) are more preferred.

  Examples of commercially available products of the above azo compounds include V-70, V-65, V-601, V-59, V-40, VF-096, V-30, VAm-110, and VAm-111 (above, Wako Pure Chemical Industries, Ltd.).

  As a commercial item of the above-mentioned peroxide, perbutyl Z, perhexa 25B (above, NOF Corporation) etc. are mentioned, for example.

  Examples of the photo radical polymerization initiator include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, imide sulfonate compounds, and the like. Among these, the radical photopolymerization initiator is at least selected from the group consisting of acylphosphine oxide compounds, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds. It is preferable that 1 type is included.

  As the above-mentioned acylphosphine oxide compound, for example, 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferable.

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

  Examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole and the like. In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The hydrogen donor means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In this embodiment, the hydrogen donor can be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable in that the sensitivity can be further improved.

  Examples of the triazine compound described above include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and ethanone-1- [9-ethyl-6. -(2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl)- 9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

  As exemplified above, as the radical photopolymerization 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.

  Commercially available products of the above-mentioned photo radical polymerization initiator include, for example, Irgacure (registered trademark) 184, 369, OX01, OX02, 819, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur (registered trademark) 1116, 1173, 4265, TPO, Lucyrin (registered trademark) TPO (above, manufactured by BASF), Ubekril P36 (manufactured by UCB), Ezacure ( Registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (above, manufactured by Fratelli Lamberti).

  (D) As content of a radical polymerization initiator, 0.05 mass part-15 mass parts are preferable with respect to 100 mass parts of (A) component, and 0.1 mass part-10 mass parts are more preferable. (D) By making content of a radical polymerization initiator into said range, the desired radical polymerization reaction can be advanced rapidly.

[(E) Fine particles]
The composition for forming a moisture trap of the embodiment of the present invention can further contain (E) fine particles. (E) Fine particles are components for imparting light scattering properties to the moisture trap of the embodiment of the present invention formed using the composition for forming a moisture trap of the present embodiment. Therefore, (E) the fine particles are preferably light scattering particles. When the composition for forming a moisture capturing body of the present embodiment contains such fine particles, the heat resistance and the light extraction efficiency can be improved.

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

As the organic particles, polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine resin beads, polycarbonate beads, polystyrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde condensate beads and the like are used. As the inorganic particles, SiO ₂ , ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O _{3 and the} like are used. These may be used alone or in combination of two or more.

  Moreover, as a commercial item of (E) microparticles | fine-particles, for example, as titania particle | grains, RTCHN15WT% -E06 made by C-I Kasei Co., Ltd. TS-149 made by Teika Co., Ltd. TIPA 15WT% -X480 made by C-I Kasei Co., Ltd. 101-20PM or the like can be used. As zirconia particles, JGC Catalysts Chemical Co., Ltd. Optolake (registered trademark) 6320Z, Nissan Chemical Co., Ltd. nano-use (registered trademark) OZ-S30K-AC, Sakai Chemical Co., Ltd. zirconia SZR-K, Solar Corporation nano5 ZR-010 Can be used.

  In the composition for forming a water trap according to the present embodiment, the (E) fine particles have an average particle diameter of 50 nm to 500 nm in the composition for forming a water trap and (E) a particle diameter of 600 nm with respect to the total amount of the fine particles. The content of the above particles is 20% by volume or less.

  (E) If the average particle size of the fine particles is less than 50 nm, a sufficient scattering effect does not appear, and the refractive index of the formed moisture trap is affected, which is not preferable. On the other hand, if it is larger than 500 nm, the scattering angle becomes narrow even if the scattering intensity (haze value) is high, so that effective scattering cannot be obtained, the light extraction efficiency is lowered, and the change of the light extraction efficiency due to the wavelength increases. The color tone tends to change, which is not preferable. More preferably, it is 50 nm-300 nm.

  (E) If the content of particles having a particle diameter of 600 nm or more with respect to the total amount of fine particles is more than 20% by volume, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. Further, since the surface roughness of the formed moisture trap is increased, there is a possibility that the film thickness unevenness or protrusions of the moisture trap may occur. The content of particles of 600 nm or more is more preferably 15% by volume or less.

  In the present invention, the “average particle size” and “particle size” of the fine particles (E) are different from the average primary particle size described later, and the moisture trapping body in consideration of the particle size of the secondary particles due to aggregation. It is the dispersed particle size in the forming composition. These can be obtained by actual measurement with an optical microscope or by a dynamic light scattering method. Here, the reason for distinguishing from the average primary particle size is that even when scattering particles having the same average primary particle size are used, the average particle size depends on the dispersion state of the fine particles in the moisture trap forming composition. This is because the particle size and particle size distribution may be different. The “average particle size” is the value of the dispersed particle size at 50% by volume of the measurement sample, and the content of particles having a particle size of 600 nm or more is the particle size of 600 nm or more of the dispersed particle size of the measurement sample. % By volume. These can be measured by “Nanotrack (registered trademark) UPA” manufactured by Nikkiso Co., Ltd. in the dynamic light scattering method.

  (E) As for the particle size distribution of the fine particles, the coefficient of variation is preferably 30% or less. The “variation coefficient” is expressed as 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 degree of variation with respect to the average particle diameter. If the coefficient of variation is greater than 30%, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. More preferably, the coefficient of variation is 20% or less.

  (E) It is preferable to use the dispersion liquid previously disperse | distributed to the solvent as the usage method.

  (E) As a method for dispersing the fine particles, a method using a dispersing agent in accordance with the surface state of the fine particles and using a disperser is preferable.

  Examples of the disperser include paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homo Mixer, homogenizer ("Clearmix (registered trademark)" manufactured by M Technique Co., Ltd.), wet jet mill ("Genus (registered trademark) PY" manufactured by Genus, "Nanomizer (registered trademark)" manufactured by Nanomizer), micro bead mill (“Super Apec Mill” and “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.) can be used.

  Here, when media are used in the above-described disperser, glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads, and the like are preferably used. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and may be implemented step by step.

  (E) In the case of inorganic particles, the average particle size and particle size distribution of the fine particles can be adjusted to a suitable range by appropriately adjusting the dispersion conditions, for example, the disperser, the dispersion medium, the dispersion time, and the dispersant. Is possible. In the case of organic particles, it can be adjusted by the synthesis conditions such as the polymerization temperature and the polymerization composition, or the dispersion conditions such as the disperser, dispersion medium, dispersion time, and dispersant.

  (E) The amount of fine particles used is preferably 1% by mass to 25% by mass and more preferably 1% by mass to 20% by mass in the composition for forming a moisture trap. If it is less than 1% by mass, a sufficient scattering effect may not appear, and if it exceeds 25% by mass, the particles tend to aggregate and the surface roughness of the moisture trap to be formed may increase.

[Additive]
The composition for forming a moisture trap according to the embodiment of the present invention may contain an additive as necessary. Specifically, a sensitizer, a curing accelerator, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, Surfactant etc. are illustrated.

[Method for Preparing Composition for Forming Moisture Capturer]
The composition for forming a moisture trap of the present invention comprises (A) component, and (B) component, if necessary (C) curable compound, (D) radical polymerization initiator, (E) fine particles and additives. Etc. can be prepared by mixing them at a predetermined ratio.

<Moisture trap>
The moisture trap of the embodiment of the present invention is formed from the composition for forming a moisture trap of the embodiment of the present invention described above.

  Since the moisture trap of the present embodiment is formed from the composition for forming a moisture trap of the embodiment of the present invention, the moisture in the electronic device applied at the time of formation is efficiently removed and also after the formation. The water in the electronic device can be consumed. Further, when the composition for forming a moisture trap body of the present embodiment contains the fine particles described above, the moisture trap body of the present embodiment is applied to an electronic device such as an organic EL element to improve the light extraction efficiency. Can do.

  And even if the moisture capturing body of this embodiment is the state which captured the moisture, it is hard to produce a decomposition product with high volatility like low molecular alcohol etc., for example, is used for electronic devices, such as an organic EL element In this case, the generation of dark spots due to the adhesion of the decomposition products to the organic EL layer can be suppressed.

  As a method for forming the moisture trap of the present embodiment, for example, after forming a coating film on a substrate such as glass using the composition for forming a moisture trap body of the embodiment of the present invention described above, Examples thereof include a method of irradiating with radiation, a method of heating, a forming method of forming by curing with a method of irradiating and heating. The radiation is not particularly limited as long as it can cure the coating film of the moisture trap forming composition, but UV (ultraviolet) light is preferable. As heating temperature, 30 to 200 degreeC is preferable and 50 to 150 degreeC is more preferable. The heating time is preferably 1 minute to 24 hours, and more preferably 10 minutes to 5 hours.

<Electronic device>
The electronic device according to the embodiment of the present invention includes the moisture trap according to the embodiment of the present invention described above. The electronic device according to the present embodiment may be any electronic device as long as moisture is an electronic device that has a possibility of deteriorating characteristics.

  The electronic device of the present embodiment includes the moisture trap of the embodiment of the present invention, so that when the moisture trap is formed from the composition for forming the moisture trap of the embodiment of the present invention, the electronic device is highly efficient. Water in the electronic device can be removed. And the water | moisture-content capture body of embodiment of this invention can absorb the water | moisture content in an electronic device over a long period of time after formation, and can suppress degradation of the electronic device resulting from a water | moisture content.

  Next, an organic EL element will be described as an example of an electronic device with reference to the drawings.

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

  An organic EL element 100, which is a first example of an organic EL element according to an embodiment of the present invention shown in FIG. And a moisture trap 30 formed in the structure 20. The moisture trap 30 is formed using the above-described composition for forming a moisture trap according to the embodiment of the present invention. The structure 20 includes a substrate 22, a sealing substrate 24, and a sealing material 26 that are substrates for elements that support the organic EL layer 10.

  Although the details of the structure of the organic EL layer 10 of the organic EL element 100 are omitted, it is sufficient that the organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other. A known structure comprising an organic light emitting layer / cathode or the like can be employed. If necessary, a charge (hole) injection layer or a charge (hole) transport layer can be provided between the anode and the organic light emitting layer, and an electron can be provided between the cathode and the organic light emitting layer. An injection layer or an electron transport layer can be provided. The organic EL layer 10 is disposed on the substrate 22 of the structure 20 as shown in FIG.

  The organic EL element 100 can have a bottom emission structure or a top emission structure. When the organic EL element 100 has a top emission structure, the organic EL layer 10 includes a back electrode serving as an anode, an organic light emitting layer, and a cathode. The translucent or semi-transparent front electrode is arranged on the substrate 22 in this order.

  In that case, the back electrode of the organic EL layer 10 preferably has light reflectivity. As the material for 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 (such as Li, Na, and K) and fluorides thereof;
Alkaline earth metals (such as Mg and Ca) and their fluorides;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals 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;
And rare earth metals such as indium and ytterbium.
A material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof, and the like can be more preferable.

  The 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 μm. For the production of the back electrode, methods such as an electron beam vapor deposition method, a sputtering method, a resistance heating vapor deposition method, and a coating method can be used. At this time, the metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Moreover, it is also possible to vapor-deposit a plurality of metals at the same time to form an alloy electrode, or an alloy prepared in advance may be vapor-deposited.

  In addition, the material of the organic light emitting layer of the organic EL layer 10 can inject holes from the anode and the like and can inject electrons from the cathode and the like when an electric field is applied, and moves the injected charge. The material is not particularly limited as long as it is a material that can form a layer having a function and a function of emitting light by providing a recombination field of holes and electrons.

The materials of the organic light emitting layer of the organic EL layer 10 are, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, Perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidins Compounds, and various metal complexes represented by metal complexes or rare earth complexes of 8-quinolinol derivatives;
and,
And polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene.

  Although the specific example of the luminescent material used as the organic light emitting layer of the organic electroluminescent layer 10 is given below, it is not necessarily limited to the following concrete examples.

  Blue light emission can be obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (TBP), a 9,10-diphenylanthracene derivative, or the like 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 9,10-bis (2-naphthyl) ) -2-tert-butylanthracene (t-BuDNA) and other anthracene derivatives. A polymer such as poly (9,9-dioctylfluorene) may also be used.

Green luminescence is produced by coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (FIrpic), and bis (2-phenylpyridinato) acetylacetonate. It can be obtained by using iridium (Ir (ppy) (acac)) or the like as a guest material. Also obtained from metal complexes such as tris (8-hydroxyquinoline) aluminum (Alq3), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) chlorogallium (Ga (mq) ₂ Cl) Can do. A polymer such as poly (p-phenylene vinylene) may also be used.

The orange to red luminescence emitted from rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (DCM1), 4- (dicyanomethylene) -2-methyl- 6- (9-Jurolidyl) ethynyl-4H-pyran (DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (BisDCM), bis [2- ( 2-thienyl) pyridinato] acetylacetonatoiridium (Ir (thp) ₂ (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (Ir (pq) (acac)) and the like are used as guest materials Obtained by. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (Znq ₂ ) or bis [2-cinnamoyl-8-quinolinolato] zinc (Znsq ₂ ). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  White light emission defines the energy level of each layer of the organic EL laminated structure and emits light using tunnel injection (European Patent No. 0390551). A light emitting element is described (Japanese Patent Laid-Open No. 3-230584), a light emitting layer having a two-layer structure is described (Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. Hei 2-216790), and a light emitting layer Are made of materials having different emission wavelengths (JP-A-4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm). Laminated and further containing a red phosphor (Japanese Patent Laid-Open No. 6-207170), blue light emitting layer contains blue fluorescent dye, green light emitting layer is red fluorescent It includes an area containing iodine, etc. construction of what (JP-A-7-142169) and the like further containing a green phosphor.

  Although the film thickness of the organic light emitting layer of the organic EL layer 10 is not particularly limited, it is usually preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.

  A method for forming the organic light emitting layer of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Broadget) method. The resistance heating vapor deposition method and the coating method are preferable.

  Further, as described above, the front electrode of the organic EL layer 10 preferably has a light-transmitting property or a semi-light-transmitting property when the organic EL element 100 has a top emission structure.

  As the material of the translucent or semi-transparent front electrode of the 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 translucent or semi-transparent front electrode material 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, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, translucency, and the like.

In addition, the front electrode of the organic EL layer 10 can be made of a light-transmitting electrode by laminating metals and ITO in order to control the electron injection property to the organic light-emitting layer while maintaining the light-transmitting property. is there. Here, the thickness of the ultrathin metal is preferably 0.1 nm to 20 nm from the viewpoint of maintaining translucency. In addition, as metals here,
Alkali metals (such as Li, Na, and K) and fluorides thereof;
Alkaline earth metals (such as Mg and Ca) and their fluorides;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals 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;
And rare earth metals such as indium and ytterbium.

  Among the above examples, the above-mentioned metals are preferably aluminum, lithium-aluminum alloy and mixed metal thereof, magnesium-silver alloy and 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 for forming the front electrode, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (such as a sol-gel method), and a solution or dispersion coating method are used. The formed front electrode is etched to form a pattern as desired. Furthermore, the driving voltage of the organic EL element can be lowered or the luminous efficiency can be increased by washing or other processing. For example, when ITO is used for the front electrode, UV-ozone treatment or the like is effective.

  Further, when the organic EL layer 10 has a hole injection layer or a hole transport layer between the anode and the organic light emitting layer, these materials have a function of injecting holes from the anode, and transport the injected holes. Any one having a function of blocking the electrons injected from the cathode may be used. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, anilines Examples thereof include copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene.

  Further, when the organic EL layer 10 has an electron injection layer or an electron transport layer between the cathode and the organic light emitting layer, the material of the electron injection layer and the electron transport layer transports electrons from the cathode. Any function may be used as long as it has a function or a function of blocking holes injected from the anode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Metal complexes of pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, silole derivatives, phthalocyanine derivatives, and 8-quinolinol derivatives; represented by metal complexes having metal phthalocyanine, benzoxazole, and benzothiazole ligands And various metal complexes.

  The thicknesses of the hole injection layer, the hole transport layer, the electron injection layer, and the electron transport layer of the organic EL layer 10 are not particularly limited, but are preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.

  A method for forming these layers of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Blodgett) method. The resistance heating vapor deposition method and the coating method are preferable.

  In the organic EL element 100 including the organic EL layer 10 having the above structure, the moisture trap 30 formed in the structure 20 is disposed separately from the organic EL layer 10 as shown in FIG. .

  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 by the sealing material 26. It has. The organic EL layer 10 is sealed with a substrate 22, a sealing substrate 24 and a 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 from an adhesive composition. Examples of the substrate 22 of the organic EL element 100 include a glass substrate, and examples of the sealing substrate 24 include a structure made of glass or the like. 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 the organic EL layer 10 can be accommodated and sealed using the sealing material 26.

  For example, when the organic EL element 100 is formed, the substrate 22 and the sealing substrate 24 are bonded to each other with a coating film made of an adhesive composition, and then the coating film is cured by irradiation and / or heating. Thus, the sealing material 26 is formed, and the organic EL layer 10 can be sealed in the sealing space.

  The moisture trap 30 formed in the structure 20 can capture moisture in the sealed space in which the organic EL layer 10 is sealed and efficiently remove it. The structure and arrangement of the moisture trap 30 are not particularly limited. For example, the moisture trap 30 is arranged on the sealing substrate 24 so as to be separated from the organic EL layer 10 like the organic EL element 100 of FIG. The Further, the moisture trap 30 may be disposed on the side surface of the organic EL layer 10 or the sealing material 26 in the sealed space. In addition, the moisture trap 30 may be laminated on the organic EL layer so as to be in close contact with the organic EL layer 10 and is disposed so as to fill the entire sealing space in the structure 20 without any gaps, as will be described later. May be.

  The organic EL element 100 having the above structure includes the moisture trap 30 to remove moisture in the element. And the organic EL element 100 can suppress the fall of the light emission characteristics, such as a brightness | luminance and light emission efficiency resulting from a water | moisture content, For example, a highly reliable organic EL lighting apparatus can be comprised. The organic EL element 100 can constitute, for example, a highly reliable organic EL lighting device.

  The organic EL element 100 can also constitute an organic EL display device. The organic EL element 100 uses, for example, a TFT substrate in which a thin film transistor (TFT) as a switching element is formed for each pixel arranged in a matrix as the substrate 22, and a plurality of organic ELs that emit a plurality of different colors. By providing the layers 10 in a matrix corresponding to the pixels, an active matrix organic EL display device can be configured.

  Hereinafter, another example of the organic EL element of the embodiment of the present invention will be described.

  FIG. 2 is a cross-sectional view schematically showing a second example of the organic EL element of the embodiment of the present invention.

  An organic EL element 200 which is a second example of the organic EL element according to the embodiment of the present invention shown in FIG. 2 has a moisture trap 130 formed in the structure 20. The moisture trap 130 is formed using the above-described composition for forming a moisture trap according to the embodiment of the present invention.

  The organic EL element 200 is different from the organic EL element 100 in FIG. 1 in that the moisture trap 130 formed in the structure 20 is formed in close contact with the organic EL layer 10. In the organic EL element 200 shown in FIG. 2, the same reference numerals are given to the same components as the organic EL element 100 of FIG.

  In the organic EL element 200, the moisture trap 130 removes moisture at the time of formation, and also prevents moisture from entering the organic EL layer 10 due to its hygroscopicity after formation. Furthermore, since the moisture trap 130 is formed so as 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 device.

  FIG. 3 is a cross-sectional view schematically showing a third example of the organic EL element of the embodiment of the present invention.

  The organic EL element 300 shown in FIG. 3 differs from the organic EL element 100 shown in FIG. 1 in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects.

  The gas barrier film 40 is provided to prevent moisture and oxygen from coming into contact with the organic EL layer 10. The gas barrier film 40 is not particularly limited and a conventionally known film can be used, and examples thereof include a film in which organic films and inorganic films are alternately laminated.

  Further, as the gas barrier film 40, US Patent Application Publication No. 2005/202646, US Patent Application Publication No. 2005/176181, US Patent Application Publication No. 2003/203210, US 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. 2010/077754 pamphlet, etc. You can also.

  The organic EL element 300 includes the gas barrier film 40 together with the moisture capturing body 30, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10. The organic EL element 300 can constitute, for example, a highly reliable organic EL lighting device.

  FIG. 4 is a cross-sectional view schematically showing a fourth example of the organic EL element of the embodiment of the present invention.

  The organic EL element 400 shown in FIG. 4 differs from the organic EL element 200 shown in FIG. 2 in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects. The gas barrier film 40 is the same as that provided in the organic EL element 300 shown in FIG.

  The organic EL element 400 includes the gas barrier film 40 together with the moisture capturing body 130, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10. The organic EL element 400 can constitute, for example, a highly reliable organic EL lighting device.

  FIG. 5 is a cross-sectional view schematically showing a fifth example of the organic EL element of the embodiment of the present invention.

  In the organic EL element 500 shown in FIG. 5, the moisture trap 30 formed from the moisture trap forming composition of the embodiment of the present invention on the organic EL layer 10 with respect to the organic EL element 400 shown in FIG. 4. And is different in that a gas barrier film 40 covering the entire surface of the moisture trap 30 and the side surface of the organic EL layer 10 is provided, and the other points are the same.

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

  Since the organic EL element 500 includes the gas barrier film 40 together with the moisture traps 30 and 130, the moisture in the element is removed and the contact of moisture with the organic EL layer 10 can be further reduced. The organic EL element 500 can constitute, for example, a highly reliable organic EL lighting device.

Hereinafter, although an embodiment of the present invention is explained in full detail based on an example, the present invention is not limitedly interpreted by this example.

<Measurement of ¹ H-NMR>
¹ H-NMR was measured at 25 ° C. using a nuclear magnetic resonance apparatus (“JNM-ECS400” (400 MHz) manufactured by JEOL Ltd.).

<[A] Synthesis of Moisture Capture Agent>
[Synthesis Example 1] Synthesis of Moisture Capture Agent (A1-i) This is an example of a compound that is the above-mentioned component (A) contained in the composition for forming a moisture trap of the present invention, that is, (A) compound ( The synthesis of each of the A1-i) compound, (A1-ii) compound, (A1-ii-2) compound, (A1-iii) compound and (A1-iv) compound will be described. In the following, these compounds are respectively referred to as a moisture trapping agent (A1-i), a moisture trapping agent (A1-ii), a moisture trapping agent (A1-ii-2), a moisture trapping agent (A1-iii), and moisture. It is called capture agent (A1-iv).

  In a 200 mL three-necked flask equipped with a condenser and a stirrer under a dry nitrogen atmosphere, 4.16 g (0.020 mol) of tetraethoxysilane and 9.628 g (0.083 mol) of 3-ethyl-3-oxetanemethanol, A catalytic amount of an aqueous potassium hydroxide solution and 50 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the ethanol and tetrahydrofuran produced by depressurizing little by little were distilled off to obtain a water scavenger (A1-i).

The generation of the moisture scavenger (A1-i) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol by ¹ H-NMR (400 MHz, acetone-d6), which is 3-ethyl-3-oxetanemethyloxy. This was done by observing a peak of δ4.5-δ3.5 derived from the group.

[Synthesis Example 2] Synthesis of moisture scavenger (A1-ii) Under a dry nitrogen atmosphere, tetraethoxysilane (4.16 g, 0.020 mol) and methacrylic acid 2 were added to a 200 mL three-necked flask equipped with a condenser and a stirrer. -10.80 g (0.083 mol) of hydroxyethyl, a catalytic amount of an aqueous potassium hydroxide solution, and 50 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the ethanol and tetrahydrofuran produced by depressurizing little by little were distilled off to obtain a water scavenger (A1-ii).

The production of the moisture scavenger (A1-ii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in ¹ H-NMR (400 MHz, acetone-d6), which is 3-ethyl-3-oxetanemethyloxy. This was done by observing a peak of δ4.5-δ3.5 derived from the group.

[Synthesis Example 3] Synthesis of Moisture Capture Agent (A1-ii-2) Under a dry nitrogen atmosphere, 4.16 g (0.020 mol) of tetraethoxysilane and a blemmer in a 200 mL three-necked flask equipped with a condenser and a stirrer PP-500 (n = 9, manufactured by NOF Corporation) 55 g (0.083 mol), a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the generated ethanol and tetrahydrofuran were distilled off gradually, and a water scavenger (A1-ii-2) was obtained.

The production of the moisture scavenger (A1-ii-2) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol by ¹ H-NMR (400 MHz, acetone-d6), 3-ethyl-3-oxetane This was done by observing a peak at δ4.5-δ3.5 derived from a methyloxy group.

[Synthesis Example 4] Synthesis of Moisture Capture Agent (A1-iii) 4.64 g (0.020 mol) of 3-methacryloyloxypropylmethyldimethoxysilane in a 200 mL three-necked flask equipped with a condenser and a stirrer in a dry nitrogen atmosphere Then, 9.628 g (0.083 mol) of 3-ethyl-3-oxetanemethanol, a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the methanol and tetrahydrofuran produced by gradually reducing the pressure were distilled off to obtain a water scavenger (A1-iii).

The generation of the moisture scavenger (A1-iii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol by ¹ H-NMR (400 MHz, acetone-d6), which is 3-ethyl-3-oxetanemethyloxy. This was done by observing a peak of δ4.5-δ3.5 derived from the group.

Synthesis Example 5 Synthesis of Moisture Capture Agent (A1-iv) 4.04 g (0.020 mol) of 3-acryloyloxypropyldimethylmethoxysilane in a 200 mL three-necked flask equipped with a condenser and a stirrer in a dry nitrogen atmosphere Then, 9.628 g (0.083 mol) of 3-ethyl-3-oxetanemethanol, a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the methanol and tetrahydrofuran produced by depressurizing little by little were distilled off to obtain a water scavenger (A1-iv).

The production of the moisture scavenger (A1-iv) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol by ¹ H-NMR (400 MHz, acetone-d6), and is produced by 3-ethyl-3-oxetanemethyloxy. This was done by observing a peak at δ4.5-3.5 derived from the group.

<Preparation of composition for forming moisture trap>
(A) Compound ((A) component), (B) Acid generator or base generator ((B) component), (C) Curability used for preparation of each moisture trap forming composition of this example The compounds ((C) component), (D) radical polymerization initiator ((D) component)) and (E) fine particles ((E) component) are shown below.

[(A) component]
A-1: Moisture trap (A1-i)
A-2: Moisture trap (A1-ii)
A-3: Moisture trap (A1-ii-2)
A-4: Moisture trap (A1-iii)
A-5: Moisture trap (A1-iv)
A-6: Aluminum triisopropoxide (Al (i-PrO) ₃ ) (manufactured by Tokyo Chemical Industry Co., Ltd.)
A-7: Calcium oxide (Tokyo Chemical Industry Co., Ltd.)

[Component (B)]
B-1: CPI-200K (manufactured by Sun Apro)
B-2: 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate B-3: Sun-Aid (registered trademark) SI-80L (manufactured by Sanshin Chemical Industry)

[Component (C)]
C-1: Epicoat (registered trademark) 828 (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.)

[(D) component]
D-1: Lucillin (registered trademark) TPO (manufactured by BASF)
D-2: V-601 (Wako Pure Chemical Industries, Ltd.)

[(E) component]
E-1: Nano-use (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Industries, Ltd. (primary particle size of zirconium oxide 20 nm, average particle size 80 nm by dynamic light scattering, solid content concentration 20% by mass),
E-2: RTCHN15WT% -E06 manufactured by CI Kasei Co., Ltd. (primary particle size of titanium oxide 25 nm, average particle size 100 nm by dynamic light scattering, solid content concentration 15% by mass)

[Example 1] (Preparation of composition for forming moisture trap (J-1))
Under an atmospheric environment, after adding 20 parts by mass of component (A-1) to 80 parts by mass of component (C-1) (C-1) to make a uniform solution, B) 1 part by mass of component (B-1) was added to prepare a moisture trap forming composition (J-1). Each component and the amount used are shown in Table 1 together with other examples described later.

[Examples 2 to 12 and Comparative Examples 1 to 4] (Preparation of Moisture Capturing Body Forming Compositions (J-2) to (J-16))
The same operation as in Example 1 was performed except that each component of the type and blending amount shown in Table 1 below was used.
Each moisture trap forming composition was prepared.

  In Examples 8 to 10 and Example 12, the [E] component was used in an amount corresponding to the solid content described in Table 1.

<Manufacture of organic EL elements>
Poly (3,4) as a hole injection material on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having an ITO film having a thickness of 15 nm formed on a glass plate having a length and width of 25 mm and a thickness of 0.7 mm and a pattern having a width of 2 mm. A coating solution for forming a hole injection layer containing ethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS) is spin-coated at 3000 rpm for 50 seconds to form a hole injection layer having a thickness of 50 nm, and then high purity. Heating and drying were performed at 200 ° C. for 10 minutes in nitrogen. Here, as the hole injection layer forming coating solution, a solution in which PEDOT / PSS was dissolved in pure water at a solid content of 0.1% by mass was used. On the hole injection layer, a 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated at 2000 rpm for 50 seconds to form an organic light emitting layer having a thickness of 70 nm, and then baked at 60 ° C. for 10 minutes. On the organic light emitting layer, 10 nm of LiF was deposited at a deposition rate of 0.1 nm / sec under a pressure condition of 10 ⁻⁵ Pa, and 20 nm of Ca was deposited at a deposition rate of 0.1 nm / sec. A cathode was formed by laminating 100 nm of Al at a deposition rate.

  Next, each of the above-mentioned compositions for forming moisture traps is applied on the organic EL layer formed on the glass substrate by spin coating, and a coating film having a thickness of 50 μm is formed by heating at 120 ° C. for 5 minutes. did. The film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation). Next, a composition having the same composition as the composition for forming moisture traps obtained in Comparative Example 1 was applied to the peripheral edge of the obtained glass substrate with a dispenser using a dispenser to form a coating film having a thickness of 100 μm. Formed.

Next, using a vacuum laminating apparatus, a counter glass substrate having a length and width of 25 mm and a thickness of 0.7 mm is bonded to the film-formed glass substrate through the coating film, and an ultrahigh pressure mercury lamp ( After irradiation with ultraviolet light (UV) of 1 J / cm ² using an intensity at 365 nm of 100 nm, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material. . Only in Example 4, using a vacuum laminating apparatus, a counter glass substrate having a length of 25 mm and a thickness of 0.7 mm was bonded to the film-formed glass substrate via the coating film, and the moisture trapping (curing) condition was 100. After heating at 30 ° C. for 30 minutes, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material.

  The organic EL element was manufactured as described above.

<Evaluation>
The film forming property of each composition for forming moisture traps of Examples 1 to 12 and Comparative Examples 1 to 4 prepared above, heat resistance of each moisture trap, glass adhesion, light emitting appearance and light extraction efficiency are as follows. Evaluation was made according to the method. The evaluation results are shown in Table 1.

[Film forming properties]
Using each prepared composition for forming moisture traps, a glass substrate having a long side of 66 mm, a short side of 24 mm, and a thickness of 1.1 mm is provided with a long side of 58 mm, a short side of 13 mm, and a depth of 0.3 mm. Then, after applying 200 μL of the moisture trap forming composition to this trench, it is cured by UV irradiation (irradiation energy: 1 J / cm ² ) using a high-pressure mercury lamp to form a moisture trap, and the appearance is visually observed. Went. At this time, when no cracks and unevenness were observed, the film-forming property was evaluated as “good”, and when at least one of cracks or unevenness was observed, the film was evaluated as defective “x”.

[Heat-resistant]
An appropriate amount of each of the prepared compositions for forming a moisture trap was put in a sample tube, and a moisture trap having a thickness of 2 mm was formed on the bottom of the sample tube under the same conditions as the above-mentioned [Film-forming property] curing conditions. Next, after exposing the formed moisture trap to the atmosphere to absorb moisture sufficiently, the lid of the sample tube is closed and sealed, and the sample tube is fixed so that the bottom of the sample tube is on top (the film-forming surface is on top). It left still in 85 degreeC environment. Thereafter, the state of the moisture trap when 336 hours passed was observed. At this time, if no change was observed in the moisture trap, the heat resistance was evaluated as “good”, and if only a slight change was observed, it was evaluated as “good”. Was evaluated as a defective “x” when deformation was observed.

[Glass adhesion]
Using each of the prepared compositions for forming a moisture trap, a glass substrate having a long side of 66 mm, a short side of 24 mm, and a thickness of 1.1 mm was used under the same conditions as the above-mentioned [Film-forming property] curing conditions, and the film thickness was 2 mm. A water trap was formed. The presence or absence of peeling of each moisture trap from the glass substrate in the air was observed. At this time, when peeling was not recognized, the adhesiveness was evaluated as “good”, and when peeled, it was evaluated as defective “x”.

[Evaluation of organic EL elements] (Evaluation of light emission appearance (dark spots, unevenness), light extraction efficiency)
About each organic EL element obtained by the above [Manufacture of organic EL elements], a forward current of 10 mA / cm ^{2 was} applied at room temperature, and the appearance of light emission (dark spots, unevenness) was observed. In addition, the front luminance was measured with a spectral radiance meter “CS-2000” manufactured by Konica Minolta Sensing Co., Ltd., and white light emission was obtained based on the front luminance of the organic EL device produced on the substrate on which the light scattering layer was not formed. The improvement rate of the front luminance of the element was calculated.

Evaluation was performed based on the following criteria.
・ Luminescent appearance (dark spots, unevenness)
Dark spots and unevenness are not observed: Good (○),
Dark spots and unevenness are observed: Impossible (×)
-Light extraction efficiency Front brightness improvement rate 1.2 times or more: Excellent (◎),
Front brightness improvement rate of 1.0 times or more and less than 1.2 times: good (◯),
Front luminance improvement rate less than 1.0 times: defective (×),

  As is apparent from the evaluation results of Table 1, in the moisture trap formed from the moisture trap forming composition of this example and the moisture trap forming composition of this example, the film forming property, heat resistance and The adhesion was good or extremely good. On the other hand, in the moisture trap formed from the composition for forming a moisture trap in the comparative example, the heat resistance was poor.

  INDUSTRIAL APPLICABILITY The present invention can provide a composition for forming a moisture trap that can be formed under the air and can form a moisture trap that hardly generates a volatile decomposition product. Therefore, the present invention can provide a water trap formed from the composition for forming a water trap and an electronic device including the water trap with high productivity, in particular, generation of dark spots. It can use suitably for electronic devices, such as an organic EL element which can be controlled.

DESCRIPTION OF SYMBOLS 10 Organic EL layer 20 Structure 22 Substrate 24 Sealing substrate 26 Sealing material 30,130 Moisture trap 40 Gas barrier film 100, 200, 300, 400, 500 Organic EL element

Claims (7)

(A) at least one compound selected from the group consisting of a siloxane compound, a titanium compound and a zirconium compound;
(B) A composition for forming a moisture trap, comprising at least one compound selected from the group consisting of an acid generator and a base generator. The compound (A) is at least one selected from the group consisting of a compound represented by the formula (A1-1) and a compound represented by the formula (A1-2). A composition for forming a moisture trap as described in 1. above.

[In the formulas (A1-1) and (A1-2), X is a silicon atom, a titanium atom or a zirconium atom; R ¹ is a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, or a 3,4-epoxy. An organic group having at least one group selected from a cyclohexyl group, a mercapto 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 ² represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon. Aromatic hydrocarbon group of formulas 6 to 14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or It is 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 composition for forming a moisture trap according to claim 1 or 2, further comprising (C) a curable compound.   (D) The composition for moisture trap formation of any one of Claims 1-3 which further contains a radical polymerization initiator.   The composition for forming a moisture trap according to any one of claims 1 to 4, further comprising (E) fine particles.   It forms from the composition for moisture trap formation of any one of Claims 1-5, The moisture trap body characterized by the above-mentioned.   An electronic device comprising the moisture trap according to claim 6.

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