KR20130141381A - Moisture-capturing agent, composition for forming moisture-capturing body, moisture-capturing body, and electronic device - Google Patents

Abstract

The present invention relates to a pellicle manufacturing method capable of reducing out gas. The pellicle manufacturing method of the present invention comprises: a step of forming a slit which is equipped with a step-shaped groove at the side of a pellicle frame by using a method of reducing SO4 ions or NH4 ions which are the out gas of the pellicle frame; a step of attaching a chemical filter and a particle filter onto the step-shaped groove; a step of attaching a first adhesive to the lower side of the pellicle frame, attaching a second adhesive to the upper side of a flat type release film (PET : polyethylene terephthalate), and arranging the flat type release film to the lower part of the pellicle frame through the first adhesive; and a step of attaching a third adhesive to the upper side of the pellicle frame and attaching a membrane to the upper part of the pellicle frame. The pellicle manufacturing method of the present invention purifies the stagnant air in the frame by the circulation of air inside the pellicle frame and fab, prevents the inflow of particles by attaching the particle filter and the chemical filter, removes gas or inorganic ions introduced into the inner space of the pellicle by absorbing the gas or inorganic ions, captures foreign materials generated in the pellicle frame during movement or the manufacture of the pellicle by attaching the second adhesive to the release film and upper side, prevents growable foreign materials form being generated in the mask arranged at the lower part of the pellicle and reduces the generation of out gas since an inner side adhesive is not used.

Description

Moisture trapping agent, composition for forming water trapping body, moisture trapping and electronic device {MOISTURE-CAPTURING AGENT, COMPOSITION FOR FORMING MOISTURE-CAPTURING BODY, MOISTURE-CAPTURING BODY, AND ELECTRONIC DEVICE}

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

For example, the organic EL device, which is a typical hermetic electronic device, is in a closed state because the light emission characteristics such as luminance and luminous efficiency are gradually lowered by moisture penetrating therein with the prolongation of the driving period. You need to use However, it is difficult to completely seal such an electronic device by sealing.

Therefore, an organic EL device is proposed which arranges a water trapping agent made of a specific organometallic compound in an electronic device in advance and maintains the inside of the electronic device in a low humidity environment (see Japanese Patent Publication No. 3936151).

However, in the water trapping agent which consists of conventional organometallic compounds, there exists a problem that adhesiveness to the board | substrate etc. of a water trapping agent are lacking. For this reason, peeling from a board | substrate etc. is concerned, and also the storage stability of the water trapping agent containing solution containing the said organometallic compound is low, and it is difficult to form a stable water trapping agent layer. Moreover, favorable film-forming property to the said board | substrate etc. and heat resistance in the environment at the time of an electronic device operation are also calculated | required.

Japanese Patent Publication No. 3936151

This invention is made | formed based on the above circumstances, The objective is the water capture | acquisition which can form the water capture body excellent in moisture absorption, heat resistance, and adhesiveness while being excellent in the film-forming property and storage stability of the composition for water trapping body formation. To provide the first.

According to an aspect of the present invention,

It is a water trapping agent (henceforth a "[A] water trapping agent") which consists of a compound (a) containing the structure represented by following formula (1):

　　

(In formula (1), R <^1> is -O-, -S-,-between the (r1) acyl group, (r2) the C1-C30 hydrocarbon group, or (r3) the carbon-carbon bond of this hydrocarbon group.) A group comprising at least one group selected from the group consisting of CO-, -CS-, -NH-, -SO- and -SO _2- , or (r4) these (r1), (r2) and (r3) A group in which a part of the hydrogen atom having the substituent is substituted with a hydroxy group, a halogen atom or a cyano group, M ¹ is a boron atom, an aluminum atom, a gallium atom, an indium atom or a tarium atom, X is an organic ligand; n Is an integer of 1 to 20; when n is 2 or more, a plurality of R ¹ , X and M ¹ may be the same or different, respectively; * ¹ and * ² represent a binding site to another site, or Or combined with each other).

In addition, another invention made to solve the above problems,

Also known as "composition for forming water trapping body (1)", comprising a water trapping agent and a compound having a polymerizable group (hereinafter also referred to as "[B] polymerizable compound"). ),

The water trapping agent and the composition for water trapping object formation containing an inorganic particle (henceforth "a composition for water trapping body formation (2)"),

A water trap formed of the composition for forming a water trap, and

An electronic device provided with the said water capture body is included.

The present invention can provide a water trapping agent capable of forming a water trapping body excellent in hygroscopicity, heat resistance and adhesion while being excellent in film formation and storage stability of the composition for forming a water trapping body. Therefore, this invention can provide the composition for water trapping body formation which can form the water capture body excellent in heat resistance, adhesiveness, etc., the water capture body formed from this composition, and the electronic device provided with the said water capture body. It can contribute to the long life of the electronic device.

1 is a cross-sectional view schematically showing an organic EL device according to a first embodiment of the present invention.
2 is a cross-sectional view schematically showing an organic EL device according to a second embodiment of the present invention.
3 is a ¹ H-NMR spectrum diagram of Compound (A) of Synthesis Example 1. FIG.
4 is a diagram showing a ¹ H-NMR spectrum of the water trapping agent (A-1) of Example 1. FIG.
FIG. 5 is a diagram showing a ¹ H-NMR spectrum of the water trapping agent (A-2) of Example 2. FIG.
FIG. 6 is a diagram showing a ¹ H-NMR spectrum of the water trapping agent (A-3) of Example 3. FIG.
7 is a diagram showing a ¹ H-NMR spectrum of the water trapping agent (A-4) of Example 4. FIG.
8 is a diagram showing a ¹ H-NMR spectrum of the water trapping agent (A-4) and the bifunctional methacrylate of Example 4. FIG.

(Mode for carrying out the invention)

<Moisture capture agent>

The water trapping agent of this invention consists of a compound (a) containing the structure represented by said formula (1). Since the said water trap agent consists of a compound (a), the water trap body containing this water trap agent has favorable hygroscopicity. This is presumed to be due to the property of M ¹ -OR ¹ possessed by compound (a) to react with water to form M ¹ -OH and the presence of an organic ligand. Hereinafter, a compound (a) is explained in full detail.

[Compound (a)]

Compound (a) is a compound containing the structure represented by said Formula (1) as mentioned above.

In said formula (1), R <^1> is -O-, -S-,-between the (r1) acyl group, (r2) C1-C30 hydrocarbon group, or (r3) carbon-carbon bond of this hydrocarbon group. A group comprising at least one group selected from the group consisting of CO-, -CS-, -NH-, -SO- and -SO _2- , or (r4) these (r1), (r2) and (r3) It is group which substituted a part of hydrogen atom which has this with a hydroxyl group, a halogen atom, or a cyano group. M ¹ is a boron atom, aluminum atom, gallium atom, indium atom or tarium atom. X is an organic ligand. n is an integer of 1-20. When n is two or more, some R <^1> , X and M <^1> may be same or different, respectively. * ¹ and * ² represent a coupling | bonding site with another site, or are mutually bonded.

As an acyl group represented by said (r1), a formyl group, an acetyl group, a propionyl group, butyryl group, isobutyryl group, t-butylacetyl group, valeryl group, isovaleryl group, pivaloyl group, lauro, for example Diary, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azeolayl group, sebacoyl group, acryloyl group , Propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, lyodoyl group, maleoyl group, fumaroyl group, citraconoyl group, mesaconoyl group, camporoyl group, benzo Diary, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatorofoil group, atorofoil group, cinnamoyl group, furoyl group, tennoyl group, nicotinoyl group, isonicortino Diary, glycoloyl group, lactoyl group, glyceroyl group, tart Noyl group, maloyl group, tartaroyl group, trofoyl group, benzylyl group, salicyloyl group, anisol group, vanilloyl group, veratroyl group, piperonylyl group, protocatecuoyl group, galloyl group, glyoxyloyl group, Pyriboyl group, acetoacetyl group, mesooxaryl group, mesooxaro group, oxalacetyl group, oxalacetyl group, levulinoyl group, etc. are mentioned. Among these, an acyl group having 3 to 30 carbon atoms is preferable, an acyl group having 4 to 20 carbon atoms is more preferable, an acyl group having 4 to 10 carbon atoms is more preferable, and a t-butylacetyl group is particularly preferable.

As a C1-C30 monovalent hydrocarbon group represented by said (r2), a C1-C30 monovalent chain hydrocarbon group, a C3-C30 monovalent alicyclic hydrocarbon group, etc. are mentioned, for example.

As carbon number of said R <^1> , 3-30 are preferable, 4-20 are more preferable, and 4-10 are more preferable. By setting the carbon number in the above range, the boiling point of hydrolysis products such as alcohol or carbonic acid derived from R ¹ generated by hydrolysis of compound (a) can be increased at the time of forming a water trap, which will be described later. Therefore, generation of outgas can be suppressed. Moreover, compatibility with the compound (a) and the compound which has a polymeric group mentioned later can also be improved. The boiling point of the hydrolysis product is preferably 150 ° C. or higher at 1 atmosphere, and 170 ° C. or higher in view of suppression of diffusion of the hydrolysis product into the electronic device when the water trapping agent is used in the electronic device. More preferably, 180 degreeC or more is more preferable.

As said C1-C30 monovalent chain hydrocarbon group, For example, linear alkyl groups, such as a methyl group, an ethyl group, n-propyl group, n-butyl group; branched alkyl groups such as i-propyl group, i-butyl group, sec-butyl group and t-butyl group; Linear alkenyl groups such as ethenyl group and n-propenyl group; Branched alkenyl groups, such as i-propenyl group and i-butenyl group, etc. are mentioned.

As said C3-C30 monovalent alicyclic hydrocarbon group, For example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group Monocyclic cycloalkyl groups such as ethylcyclohexyl group; Monocyclic cycloalkenes, such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, a cyclopentadienyl group, a cyclohexadienyl group, a cyclooctadienyl group, and a cyclodecadiene Nyl group; Bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl, tricyclo [5.2.1.0 ^2,6 ] decyl, tricyclo [3.3.1.1 ^3,7 ] decyl, tetracyclo [6.2 .1.1 ^3,6 .2 ^2,7 ] polycyclic cycloalkyl groups such as dodecyl group, norbornyl group and adamantyl group.

Examples of the group represented by (r3) include R ^A -LR ^B- , R ^A -LR ^B -LR ^B -and the like. R ^A is a monovalent hydrocarbon group. R ^B is a divalent hydrocarbon group. Examples of the R ^A, for example, there may be mentioned a monovalent hydrocarbon group and the same group and the like exemplified as the above R ^1. Examples of the R ^B, for example, there may be mentioned groups except one hydrogen atom from a monovalent hydrocarbon group represented by R ^A. L is a group selected from the group consisting of -O-, -S-, -CO-, -CS-, -NH-, -SO-, and -SO _2- .

As a halogen atom of the substituent which the group represented by said (r1), (r2), and (r3) may have, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

As said R <^1> , an acyl group is preferable and group represented by following formula (2) is more preferable among acyl groups. In view of these groups, R ¹ can reduce the outgas and improve compatibility with a compound having a polymerizable group.

In said Formula (2), R <^2> , R <^3> and R <^4> respectively independently represents a C1-C12 monovalent hydrocarbon group or a part of the hydrogen atom which this hydrocarbon group has a hydroxyl group, a halogen atom, or a cyano group It is group substituted by. q is an integer of 0-6. * ³ represents a bonding site with an oxygen atom.

As a C1-C12 monovalent hydrocarbon group represented by said R <^2> , R <^3> and R <^4> , a C1-C12 monovalent chain hydrocarbon group, a C3-C12 monovalent alicyclic hydrocarbon group, etc. are mentioned, for example. Can be mentioned.

As said C1-C12 linear hydrocarbon group, a C1-C12 thing etc. are mentioned among the monovalent chain hydrocarbon groups illustrated as R <^1>, for example.

As said C3-C12 monovalent alicyclic hydrocarbon group, a C3-C12 thing etc. are mentioned in the monovalent alicyclic hydrocarbon group illustrated as R <^1>, for example.

The organic ligand represented by X has an atom having an isolated electron band and coordinates with the atom represented by M ¹ as a coordinating atom to form a complex.

As a coordinating atom of the said organic ligand, it is preferable that it is at least 1 sort (s) chosen from the group which consists of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom, More preferably, an oxygen atom and a nitrogen atom are more preferable. By making a coordinating atom into the said atom, the said coordination bond can be made stronger, As a result, the adhesiveness of the water trapping agent containing the said water trapping agent can be improved more. For example, when a water trapping body is formed on a substrate used for an electronic device or the like, the adhesion of the water trapping body to a substrate can be further improved.

It is preferable that the said organic ligand is at least 1 sort (s) chosen from the group which consists of a compound which has a heterocyclic ring, the compound which has an ester group, the compound which has an amide group, and the compound which has an amino group. By making an organic ligand into the said compound, the said coordination bond can be made stronger. In addition, the organic ligand in the said compound (a) may be 1 type, or 2 or more types.

Examples of the compound having a heterocycle include furan, thiophene, pyrrole, 2H-pyrrole, 2H-pyran, 4H-thiopyran, pyridine, oxazole, isoxazole, thiazole, isothiazole and furazane. , Imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indole, isoindole, indolizine, carbazole, benzimidazole, quinoline And compounds represented by the following formula (K1-1), compounds represented by the following formula (K1-2), and the like.

As a compound which has a heterocycle, pyridines and the compound represented by said formula (K1-1) are preferable in these.

As a compound which has the said ester group, the compound which has an ester group and the (meth) acryloyloxy group which has a polymerizable double bond is preferable. Examples of the compound having a (meth) acryloyloxy group include a polyfunctional (meth) acrylate compound having two or more (meth) acryloyloxy groups in a molecule and a group having one (meth) acryloyloxy group in a molecule. A functional (meth) acrylate compound is mentioned.

As said polyfunctional (meth) acrylate compound, for example, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate , Tricyclodecanediyl dimethylenedi (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydr Oxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylol propane tri (meth) acrylate, EO modified trimethylol Propane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (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 ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylic Latex, caprolactone modified dipentaerythritol penta (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylic (Meth) acrylate of phenol novolak polyglycidyl ether, 1, 3-bis ((meth) acryloyloxy) -2-propanol, 9, 9-bis [4- [2- (acrylo) Iloxy) ethoxy] phenyl] -9H-fluorene etc. are mentioned. As polyfunctional (meth) acrylate, among these, polypropylene glycol di (meth) acrylate is preferable.

As a commercial item of the said polyfunctional (meth) acrylate compound, For example, Viscoat # 195, Copper # 230, Copper # 260, Copper # 335HP, Copper # 540, Copper # 700 (above, Osaka Organic Chemical Industry Co., Ltd.), TMPT, 9G, 9PG, 701, BPE-500, DCP, DOD-N, HD-N, NOD-N, NPG (above, Shin-Nakamura Chemical Co., Ltd.), etc. are mentioned.

As said monofunctional (meth) acrylate compound, it is (meth) acryloyl morpholine, 7-amino-3,7- dimethyloctyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, for example. Isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, Uryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetra Chlorophenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 Hydro Cipropyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( Meth) acrylate, isobornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxy Methoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, (meth) acrylate of p-cumylphenol reacted with ethylene oxide, 2-bromophenoxyethyl (meth) acrylate, 4-bro Mophenoxyethyl (meth) acrylate, 2,4-dibromo Phenoxyethyl (meth) acrylate, 2,6-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-tribromo Phenoxyethyl (meth) acrylate etc. are mentioned.

Examples of the compound having the amide group include N, N-dimethylformamide, N, N'-diacetylethylenediamine, N, N'-diacetyltrimethylenediamine, and N, N'-diacetyltetramethylenediamine , N, N'-diacetylpropylenediamine, N, N'-diacetylhexamethylenediamine, N, N'-diacetyloctamethylenediamine, 1,3,5-tripropanoylhexahydro-s-triazine , Acrylamide, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, vinyl caprolactam, N-vinylpyrrolidone and the like. As a compound which has an amide group, N, N- dimethylformamide is preferable among these.

Examples of the compound having an amino group include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, tert-butylamine, pentylamine, hexylamine, isopentylamine, neopentylamine, octylamine, and decylamine. , Dodecylamine, a compound represented by the following formula (K2-1), a compound represented by the following formula (K2-2), and the like.

Examples of the organic ligand include pyridine, N, N-dimethylformamide, N, N'-diacetylethylenediamine, N, N'-diacetyltrimethylenediamine, N, N'-diacetyltetramethylenediamine, N, N '-Diacetylpropylenediamine, N, N'-diacetylhexamethylenediamine, N, N'-diacetyloctamethylenediamine, 1,3,5-tripropanoylhexahydro-s-triazine, polypropylene glycol Di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the compound represented by said formula (K1-1), (K1-2), (K2-1) and (K2-2) are preferable, , Pyridine, N, N-dimethylformamide, polypropylene glycol di (meth) acrylate, and the compound represented by the formula (K1-1) are more preferred, and among them, the composition for forming water trapping bodies (1) or ( Polypropylene glycol di (meth) acryl which has a polymerizable double bond from a viewpoint of improving the bondability between the compounds which 2) contains Sites are more preferred.

M ¹ is a boron atom, aluminum atom, gallium atom, indium atom or tarium atom. Covalently bonded compounds comprising these Group 13 elements that do not satisfy the octet rule are strong Lewis acids and are capable of forming coordinating bonds with organic ligands. Among these, as M ¹ , an aluminum atom is preferable. When M ¹ is an aluminum atom, stronger coordination bonds can be formed with the organic ligand.

And atoms represented by the above M ^1, a combination of atoms and other than the organic ligand is bonded to M ¹ atom represented by this is, an ionic bond, covalent bond, and no matter which of the coordinate bond would.

In the formula (1) * ¹ and * ² in the structure represented by, respectively, may be bonded univalent group such as an organic group, the * ¹ and * ² are bonded to each other but may form a ring structure, wherein * ¹ And * ² are preferably bonded to each other to form a ring structure.

As the compound (a), it is preferable to include a cyclic aluminoxane compound having a reduced number of 6 (hereinafter, the cyclic aluminoxane compound is also referred to as a "specific cyclic aluminoxane compound"). When the water trap is composed of the specific cyclic aluminoxane compound, the water trap obtained from the water trap has excellent adhesiveness and the like.

It is preferable that this specific cyclic aluminoxane compound is a compound obtained by making the said organic ligand react with the cyclic aluminoxane of reduced water 6.

As said specific cyclic aluminoxane compound, the compound represented by following formula (a1)-(a3) is mentioned.

In said formula, R <^1> and X are synonymous with said Formula (1).

The specific cyclic aluminoxane compound may be any single compound among the compounds represented by the formulas (a1) to (a3) or a mixture containing two or more compounds among the compounds represented by these (a1) to (a3). good. When the said specific cyclic aluminoxane compound is a mixture, R <^1> and X which are said 2 or more types of compounds may respectively differ.

<Synthesis method of compound (a)>

As a method for synthesizing the compound (a), for example, an organometallic compound containing a metal of Group 13 of the periodic table such as a boron atom and an aluminum atom is condensed while heating to form an oligomer, and the resulting oligomer and pyridine, N, The method of reacting and synthesizing organic ligands, such as N-dimethylformamide, etc. are mentioned.

<Composition for forming water trapping body (1)>

The composition for moisture trapping body formation (1) of this invention contains the [A] moisture trapping agent and a [B] polymeric compound. In addition, the composition for moisture trapping body formation (1) may contain a [C] polymerization initiator as a suitable component. Moreover, the composition for water trapping body formation (1) may contain other arbitrary components in the range which does not impair the effect of this invention. Each component will be described in detail below.

[[A] Moisture Capture Agent]

The water trap (A) consists of the compound (a) containing the structure represented by said formula (1). In addition, since a compound (a) is mentioned above in the term of the <water trapping agent>, detailed description here is abbreviate | omitted.

As content of the water trap (A), 5 mass% or more and 50 mass% or less are preferable, and 10 mass% or more and 50 mass% or less are more preferable. By setting the content of the water trapping agent (A) in the above range, the hygroscopicity of the water trapping body described later can be effectively increased, and the film forming property of the composition for forming water trapping body (1) can be improved by an appropriate viscosity. .

[[B] Polymerizable compound]

The polymerizable compound (B) is a compound having a polymerizable group. When the composition for forming water trapping bodies (1) contains the polymerizable compound [B], the crosslinking reactivity of the composition for forming water trapping bodies (1) can be increased, and the composition for forming water trapping bodies (1) is formed. The strength and adhesiveness of the water trapping body can be further improved. For example, when a water trapping body is formed in a film form on a substrate used for an electronic device or the like, the film strength of the water trapping body and adhesion to the substrate can be further improved. In addition, as a composition (1) for water trapping body formation, you may use [B] polymeric compound individually or in combination of 2 or more types. The polymerizable compound [B] may be the same as or different from the organic ligand of the compound (a).

Examples of the polymerizable compound (B) include a compound having a cyclic ether group, a compound having a polymerizable double bond, and the like.

As a compound which has the said cyclic ether group, the compound which has an epoxy group, the compound which has an oxetanyl group, etc. are mentioned, for example.

As a compound which has the said epoxy group, it is, 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-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl Etc

As a polyfunctional epoxy compound,

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol AD diglyl Polyglycidyl ethers of bisphenols such as cylyl ether;

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

Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or two 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-meth-di Oxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene Compounds having 3,4-epoxycyclohexyl groups, such as bis (3,4-epoxycyclohexanecarboxylate) and lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate Can be mentioned.

As a compound which has the said oxetanyl group, for example,

As a monofunctional oxetane compound,

3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyl oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dodecyl Oxymethyl) 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-ethyloxetan-3-yl) methoxymethyl] butane, 3-ethyl-3 {[(3-ethyloxetane-3- And 1) methoxy] methyl} oxetane and 1,1,1-tris [(3-ethyloxetan-3-yl) methoxymethyl] propane.

As a compound which has the said cyclic ether group, from a viewpoint of improving crosslinking reactivity, a polyfunctional epoxy compound and a polyfunctional oxetane compound are preferable, and a polyfunctional oxetane compound is more preferable, and 3-ethyl-3 {[( More preferred is 3-ethyloxetan-3-yl) methoxy] methyl} oxetane.

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

As said (meth) acrylate compound, For example, the same compound as the (meth) acrylate compound illustrated as monofunctional (meth) acrylate and polyfunctional (meth) acrylate in description of the above-mentioned organic ligand, etc. Can be mentioned.

As a compound which has the said polymerizable double bond, from a viewpoint of improving crosslinking reactivity, a polyfunctional (meth) acrylate compound is preferable among these, a polyfunctional methacrylate compound is more preferable, and a polypropylene glycol dimethacryl The rate is more preferable, and polypropylene glycol # 400 dimethacrylate is particularly preferable.

As said polymeric group, it is more preferable that it is a cyclic ether group. When the said polymerizable group is a cyclic ether group, the crosslinking reactivity of [B] polymeric compound can be heightened more.

As content of the polymeric compound (B), 50 mass parts or more and 1,000 mass parts or less are preferable with respect to 100 mass parts of [A] moisture trapping agents, and 100 mass parts or more and 500 mass parts or less are more preferable. By making content of a polymerizable compound (B) into the said range, adhesiveness to the board | substrate etc. of the electronic device of the water trapping body formed can be raised effectively.

[[C] polymerization initiator]

[C] The polymerization initiator is a component which decomposes by light irradiation and / or heating to generate active species for generating a polymerization reaction of the [B] polymerizable compound.

[C] As the polymerization initiator, for example, a photoacid generator that absorbs light to generate an acid as the active species, radical polymerization initiators such as azo compounds and peroxides that decompose by light irradiation or heating to generate radicals as the active species. Etc. can be mentioned. When the polymerizable compound (B) is a compound having a cyclic ether group, a radical polymerization initiator is suitably used when the photoacid generator is a compound having the polymerizable double bond (B).

As said photo-acid generator, the compound represented by following formula (3) is preferable.

In said formula (3), E <^-> is an anion.

Examples of the anion represented by, for example, SbF ₆ ^{- -} wherein E, PF ₆ ^-, can be given other anions such as turned over.

As a commercial item of the said photo-acid generator, CPI-100P, CRI-101A, CPI-200K, CPI-210S (above, San Afro) etc. are mentioned, for example.

Examples of the azo compound 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), 2,2'- azobis (N-cyclohexyl-2-methylpropionamide), etc. are mentioned. Among them, dimethyl-2,2'-azobis (2-methylpropionate) is preferred.

As a commercial item of the said azo compound, For example, V-70, V-65, V-601, V-59, V-40, VF-096, V-30, VAm-110, VAm-111 (above, Waco Pure chemical industry manufacture) etc. are mentioned.

As said peroxide, t-butyl peroxy benzoate, 2, 5- dimethyl- 2, 5- di (t-butyl peroxy) hexane, etc. are mentioned, for example.

As a commercial item of the said peroxide, perbutyl Z, perhexa 25B (above, Nichi oil make), etc. are mentioned, for example.

As content of the [C] polymerization initiator, 0.05 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of [B] polymeric compounds, and 0.1 mass part or more and 2 mass parts or less are more preferable. By making content of a polymerization initiator (C) into the said range, while carrying out a superposition | polymerization reaction rapidly, the bad influences, such as a fall of adhesiveness to the board | substrate of an electronic device, etc. of the water trapping body formed can be suppressed. In addition, you may use a [C] polymerization initiator individually or in combination of 2 or more types.

<Other optional components>

As other arbitrary components, stabilizers, inorganic particles, etc. are mentioned, for example. You may use these other arbitrary components individually or in combination of 2 or more types. Each component will be described below.

[stabilizator]

A stabilizer is a component which reduces gelation of the composition for water trapping body formation (1), and improves storage stability.

As said stabilizer, a hydroquinone compound, a phenol compound, etc. are mentioned, for example. As said hydroquinone compound, hydroquinone monomethyl ether etc. are mentioned, for example. As said phenolic compound, 4-tert- butylcatechol, butylhydroxyanisole, 3, 5- dibutylhydroxy toluene, DL- (alpha)-tocopherol, N-nitrosophenyl hydroxyamine aluminum salt, etc. are mentioned, for example. Can be mentioned.

As content of the said stabilizer, 10 mass ppm-500 mass ppm are preferable, and 50 mass ppm-300 mass ppm are more preferable. By making the content rate of a stabilizer into the said range, the storage stability of the composition for water trapping body formation (1) can be raised effectively.

[Inorganic Particles]

As an inorganic particle, a well-known thing can be used and the same thing as [D] inorganic particle of the composition for water trapping object formation mentioned later can be used. In addition, content of an inorganic particle and an effect are basically the same as that of [D] inorganic particle. Since the inorganic particle (D) is explained in full detail later, the detailed description of the inorganic particle as an arbitrary component of the composition for water trapping body formation (1) here is abbreviate | omitted.

<Composition for forming water trapping body (2)>

The composition for moisture trapping body formation (2) of this invention contains the [A] moisture trapping agent and [D] inorganic particle. In addition, the composition for moisture trapping body formation (2) may contain other arbitrary components, such as the said stabilizer, in the range which does not impair the effect of this invention. Each component will be described in detail below.

[[A] Moisture Capture Agent]

The water trap (A) consists of the compound (a) containing the structure represented by said formula (1). In addition, since a compound (a) is mentioned above in the term of the <water trapping agent>, detailed description here is abbreviate | omitted.

As content of the water trap (A), 5 mass% or more and 50 mass% or less are preferable, and 10 mass% or more and 50 mass% or less are more preferable. By making content of the water trapping agent (A) into the said range, the hygroscopicity of the water trapping body mentioned later can be improved effectively, and the film-forming property of the composition for water trapping body formation (2) can be improved by moderate viscosity. .

[[D] Inorganic Particles]

The inorganic particle (D) is a component which raises the refractive index of the water trapping body formed, or improves heat dissipation. If the refractive index can be increased, the light extraction efficiency from the light emitting layer can be improved. In addition, electronic devices such as an organic EL illuminating device in which a plurality of organic EL elements are arranged may generate heat, and due to the increase in temperature in the vicinity of the element, there is a problem that adversely affects light emission characteristics such as luminance and luminous efficiency. It may occur. Therefore, when the composition for forming a water trapping body contains the inorganic particles, the heat dissipation of an electronic device such as an organic EL lighting device having a water trapping body is increased, thereby protecting it from moisture and preventing the harmful effects of heat generation. Can protect.

As said inorganic particle, a well-known thing can be used. By containing the inorganic particles in the composition for forming the water trapping body (2), not only the thermal conductivity of the water trapping body formed using the composition for forming the water trapping body (2) is improved, but the compound (a) described above is used for moisture absorption. The component (decomposition product) which decomposes | disassembles and generate | occur | produces by adsorb | sucking can be adsorbed, and this decomposition product can be trapped in the inside of a water trapping body. Thereby, the said decomposition product can be prevented from acting as a plasticizer of a water trapping body, and it does not deform | transform by heat flow even in the use environment exceeding 80 degreeC, for example. Moreover, as another function of the said inorganic particle, improving the mechanical strength of the water trapping body formed using the composition for water trapping body formation (2), increasing the moisture absorption ability of this water trapping body, etc. are mentioned.

As a material of the said inorganic particle, a metal oxide and a metal nitride are preferable. Examples of the metal oxides include silica (including silica gel), smectite, zeolite, alumina, titanium oxide, zirconia, magnesia, barium titanate, and various glass powders used for heat dissipating materials. As metal nitride, boron nitride, aluminum nitride, silicon nitride, etc. are mentioned, for example. In addition to the metal oxides and metal nitrides, silicon carbide, boron carbide, and activated carbon may also be used as the inorganic particles. Among these, it is preferable that it is at least 1 sort (s) of particle | grains chosen from the group which consists of alumina, a silica, boron nitride, aluminum nitride, silicon nitride, magnesia, silicon carbide, boron carbide, and smectite from a viewpoint of suppressing heat fluidity, and furthermore, From the viewpoint of excellent thermal conductivity, particles of alumina and / or boron nitride are more preferable.

As average particle diameter of the said inorganic particle, 5 nm-5,000 nm are preferable, 5 nm-2,000 nm are more preferable, 5 nm-500 nm are still more preferable, 5 nm-100 nm are especially preferable. By making the average particle diameter of an inorganic particle into the said range, the deformation | transformation by the heat flow of the water capture body formed from the composition for water trapping body formation (2) can be prevented, and especially if an average particle diameter is 5 nm-100 nm, transparency It is also possible to form excellent water traps. Moreover, when the average particle diameter of an inorganic particle exists in the said range, it becomes easy to give a suitable viscosity as mentioned later to the composition for water trapping body formation (2), and workability at the time of forming a water trapping agent (coating property) Etc.) becomes favorable. Moreover, when the average particle diameter of an inorganic particle exists in the said range, it will have sufficient surface area for an inorganic particle to capture | decompose a decomposition product, and, thereby, the deformation | transformation by the heat flow of a water trapping body can be suppressed.

As content of an inorganic particle, from a viewpoint of improving the thermal conductivity of a water trapping body, 0.1 mass%-80 mass% are preferable, and 20 mass%-60 mass% are more preferable. Moreover, from a viewpoint of ensuring transparency of a water trapping body, 0.1 mass%-20 mass% are preferable, and 0.1 mass%-10 mass% are more preferable. Moreover, if content of an inorganic particle is 0.1 mass% or more, the water trapping body which does not deform | transform by heat flow can be obtained.

Moreover, it is preferable that one of the composition (1) and (2) for water trapping body formation contains three components, a [A] water trap, a [B] polymeric compound, and [D] inorganic particle.

<Preparation method of the composition for water trapping body formation (1) and (2)>

The composition for moisture trapping body formation (1) can be prepared by mixing [A] a water trapping agent and a [B] polymeric compound, a [C] polymerization initiator, a stabilizer, an inorganic particle, etc. as needed at a predetermined ratio. .

The composition for water trapping body formation (2) can be prepared by mixing [A] water trapping agent, [D] inorganic particle, stabilizer, etc. as needed at a predetermined ratio.

<Moisture trap>

The water trapping body of this invention is formed from the composition (1) or (2) for water trapping body formation. Since this water trapping body is formed from the composition (1) or (2) for water trapping body formation, it is excellent in hygroscopicity, heat resistance, adhesiveness with the board | substrate, etc. of an electronic device.

As a formation method of the said water trapping body, after forming a coating film on substrates, such as glass, using the composition for water trapping body formation (1) or (2), this coating film is irradiated and / or The method of hardening | curing by heating and forming a moisture trap, etc. are mentioned. The radiation is not particularly limited as long as the coating film can be cured, but UV light is preferable. As heating temperature, 30 to 200 degreeC is preferable and 50 to 150 degreeC is more preferable. As heating time, 1 minute-24 hours are preferable, and 10 minutes-5 hours are more preferable.

<Electronic device>

The electronic device of this invention is equipped with the said water capture body. The electronic device may be any electronic device as long as it is an electronic device vulnerable to moisture. By providing the said water trapping object, the said electronic device can absorb the moisture in an electronic device, and can suppress the deterioration of the element resulting from moisture. Hereinafter, an example of the organic electroluminescent element which is a typical sealed electronic device is demonstrated, referring drawings.

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

As shown in FIG. 1, the organic EL element 100 includes an organic EL layer 10, a structure 20 for storing the organic EL layer 10 and blocking it from outside air, and the structure 20. ), A water trap 30 is formed.

The organic EL layer 10 may be a structure in which an organic light emitting material layer made of an organic material is sandwiched between a pair of electrodes facing each other. For example, an anode / charge (hole) transporting agent / Known structures, such as a light emitting layer / cathode, can be taken.

The water trapping body 30 is formed apart from the organic EL layer 10. As described above, the water trapping body 30 is formed of the composition for forming water trapping bodies (1) or (2) containing the water trapping agent.

The structure 20 is equipped with the board | substrate 22, the sealing cap 24, and the adhesive agent 26. As the board | substrate 22, the structure etc. which consist of glass are mentioned as the sealing cap 24, such as a glass substrate. In addition, the structure of the structure 20 should just be able to accommodate the organic EL layer 10, and is not specifically limited.

2 is a cross-sectional view schematically showing an organic EL element 200 according to a second embodiment of the present invention. In addition, in FIG. 2, the same code | symbol is attached | subjected to the same thing as the element of the organic electroluminescent element 100 of FIG.

As shown in FIG. 2, the organic EL element 200 is formed such that the water trapping body 40 formed in the structure 20 is brought into close contact with the organic EL layer 10. Is different. In this case, the moisture trapping body 40 can prevent the ingress of moisture into the organic EL layer 10 due to its hygroscopicity, and can also protect the organic EL layer 10. By using an inorganic, organic, organic inorganic lamination barrier film, or the like, deterioration of the device due to the influence of moisture can be further prevented.

[Example]

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. It shows below about the measuring method of the physical property in a present Example.

¹ H-NMR analysis

¹ H-NMR analysis was performed under the conditions of measurement frequency: 400 MHz and measurement solvent: toluene -d 8 using a nuclear magnetic resonance apparatus (JNM-ECX400, manufactured by Nippon Electronics).

<Synthesis of [A] Moisture Capture Agent>

Synthesis Example 1 (Synthesis of Compound (A))

Into a 1 L four-necked flask, 81.7 g (0.40 mol) of aluminum triisopropoxide and AF-7 solvent (manufactured by JX Nikko-Niseki Energy Co., Ltd.) as a solvent were added and heated to 120 ° C to 130 ° C while stirring. Subsequently, the mixed solution of 2.70 g (0.15 mol) of water, 27.9 g (0.24 mol) of tert-butyl acetic acid, and 24.3 g of isopropanol was poured into this solution in 2 hours, leaving by-product isopropanol. It was dripped over and reacted.

Subsequently, this reaction liquid was heated to 180 degreeC, and the mixed solution of 0.90 g (0.050 mol) of water, 9.29 g (0.08 mol) of tert-butyl acetic acid, and 8.10 g of isopropanol was dripped over 30 minutes, spilling by-produced isopropanol. The reaction was carried out.

Subsequently, the reaction solution was heated to 190 ° C., and a mixed solution of 3.60 g (0.20 mol) of water, 9.29 g (0.08 mol) of tert-butylacetic acid, and 32.4 g of isopropanol was released for 1 hour and 30 minutes while flowing by-produced isopropanol. It was dripped over and reacted.

Subsequently, the flask was depressurized to remove isopropanol, and AF-7 solvent was further distilled off under conditions of 150 ° C and 266 kPa. Then, the obtained white to fine yellow foamy compound was pulverized to obtain 63.3 g (yield 95%) of white powdery compound (A). The obtained compound (A) is tris (3,3-dimethylbutyrate) cyclotrialumino acid represented by the following formula (A).

The spectrum of the ¹ H-NMR analysis of this tris (3,3-dimethylbutyrate) cyclotrialumino acid is shown in FIG. 3.

^As a result of the ¹ H-NMR analysis, δ = 2.70-2.10 (brs) and 1.80-0.70 (m).

 Example 1 Synthesis of Moisture Capture Agent (A-1)

47.4 g (about 0.1 mole) of Compound (A) obtained in Synthesis Example 1 was dissolved in 100 mL of hexane, 7.91 g (0.1 mole) of pyridine was added, and the mixture was stirred at 30 ° C. for 1 hour under a nitrogen atmosphere. Subsequently, hexane was distilled off under the conditions of 50 degreeC and 266 Pa, and 53.7 g (yield 97%) of water trapping agents (A-1) of white to pale yellow powder shape were obtained.

This water trap (A-1) is a tris (3,3-dimethylbutyrate) cyclotrialuminoacid pyridine complex in which pyridine is assigned to the aluminum atom of the compound (A).

The spectrum of the ¹ H-NMR analysis of the water trapping agent (A-1) is shown in FIG. 4.

^As a result of ¹ H-NMR analysis, δ = 8.52 (d, J = 3.7 kV), 7.04 (tt, J = 7.4, 1.8 kV), 6.73 (t, J = 7.4 kV), 2.70-2.10 (brs), 1.80 -0.70 (m).

Example 2 Synthesis of Moisture Capture Agent (A-2)

47.4 g (about 0.1 mole) of Compound (A) obtained in Synthesis Example 1 was dissolved in 100 mL of hexane, 7.31 g (0.1 mole) of N, N-dimethylformamide was added thereto, and the mixture was stirred at 30 ° C. for 1 hour under a nitrogen atmosphere. did. Subsequently, hexane was distilled off under the conditions of 50 degreeC and 266 Pa, and 51.5 g (yield 94%) of water trapping agents (A-2) of white to pale yellow powder shape were obtained.

The water trapping agent (A-2) is a tris (3,3-dimethylbutyrate) cyclotrialumino acid N, N-dimethylformamide in which N, N-dimethylformamide is distributed to the aluminum atom of the compound (A). It is a complex.

The spectrum of the ¹ H-NMR analysis of the water trapping agent (A-2) is shown in FIG. 5.

^As a result of the ¹ H-NMR analysis, δ = 7.67 (s), 2.42 (s), 2.06 (s), 2.70-2.10 (m) and 1.80-0.70 (m).

Example 3 (Synthesis of Moisture Capture Agent (A-3))

47.4 g (about 0.1 mole) of Compound (A) obtained in Synthesis Example 1 was dissolved in 100 mL of hexane, 9.91 g (0.05 mole) of 1,3-di (4-pyridyl) propane was added, and under a nitrogen atmosphere, 30 It stirred at 1 degreeC. Subsequently, hexane was distilled off under the conditions of 50 degreeC and 266 Pa, and 56.7 g (yield 99%) of water trapping agents (A-3) of white to pale yellow powder shape were obtained.

The water trapping agent (A-3) is a tris (3,3-dimethylbutyrate) cyclotrialuminoacid 1, in which 1,3-di (4-pyridyl) propane is assigned to an aluminum atom of the compound (A). 3-di (4-pyridyl) propane complex.

The spectrum of the ¹ H-NMR analysis of the water trapping agent (A-3) is shown in FIG. 6.

^As a result of the ¹ H-NMR analysis, δ = 8.53 (s), 6.63 (s), 2.11 (m), 2.70-2.10 (m) and 1.80-0.70 (m).

Example 4 Synthesis of Moisture Capture Agent (A-4)

47.4 g (about 0.1 mole) of Compound (A) obtained in Synthesis Example 1 was dissolved in 100 mL of hexane, 26.8 g (0.05 mole) of polypropylene glycol ＃ 400 dimethacrylate, which became an organic ligand, was added, and under a nitrogen atmosphere, It stirred at 30 degreeC for 1 hour. Subsequently, hexane was distilled off under the conditions of 50 degreeC and 266 Pa, and 74.2 g (yield 100%) of high viscosity liquid trapping agents (A-4) were obtained.

The water trapping agent (A-4) is a tris (3,3-dimethylbutyrate) cyclotrialuminoxane polypropylene glycol # 400 in which polypropylene glycol # 400 dimethacrylate is distributed to the aluminum atom of the compound (A). Dimethacrylate complex. The structure in which the polypropylene glycol # 400 dimethacrylate of the aluminum reactor in this water trapping agent (A-4) is coordinated is shown by following formula (II).

The spectrum of the ¹ H-NMR analysis of the water trapping agent (A-4) is shown in FIG. 7.

As a result of ¹ H-NMR analysis of the water trapping agent (A-4), δ = 6.13 (s), 5.24 (s), 5.21-5.10 (m), 3.60-3.10 (m), 2.70-2.10 (m), 1.86 (s) and 1.80-0.70 (m).

8, the spectrum of the ¹ H-NMR analysis of polypropylene glycol # 400 was overlapped and shown. In addition, in FIG. 8, the tris (3, 3- dimethyl butyrate) cyclotrialuminate polypropylene glycol # 400 dimethacrylate complex is described as "aluminum complex", and polypropylene glycol # 400 dimethacrylate is "2." Functional methacrylate ”.

From the ¹ H-NMR spectrum of FIG. 8, the peak of the bifunctional methacrylate (corresponding to the formula (II)) coordinated to the aluminum complex is non-coordinated by the coordination. It confirmed that it shifted from the peak of correspondence to I).

<Preparation of the composition for moisture trapping body formation>

The [B] polymeric compound and [C] polymerization initiator used for preparation of each composition for water trapping body formation are shown below.

[[B] Polymerizable compound]

B-1: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (OXT221, manufactured by Toagose)

B-2: Polypropylene glycol # 400 dimethacrylate (9PG, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[[C] polymerization initiator]

C-1: 4- (phenylthio) phenyldiphenylsulfonium salt (CPI-200K, produced by San Afro)

C-2: diethyl 2,2'- azobis (2-methylpropionate) (V-601, Wako Pure Chemical Industries Ltd. make)

Example 5 (Preparation of Composition for Moisture Capture Form (J-1))

In a glove box having a dew point of −60 ° C. or less and 5 ppm or less of oxygen, 25 parts by mass of (A-1) as a water trapping agent is added to 75 parts by mass of (B-1) as a [B] polymerizable compound and uniform. After making it the solution, 0.1 mass part of (C-1) as a [C] polymerization initiator was added to this solution, and the composition for water trapping object formation (J-1) was prepared.

[Examples 6 to 10 and Comparative Examples 1 and 2] (Preparation of Compositions for Forming Moisture Capture (J-2) to (J-6) and (j-1) to (j-2))

Except having used each component of the kind and compounding quantity shown in following Table 1, it operated like Example 5, and prepared each composition for water trapping body formation. In addition, "-" in Table 1 shows that the corresponding component was not mix | blended.

<Formation of Moisture Capture>

[Example 11]

A long side of 58 mm, a short side of 13 mm, and a depth of 0.3 mm were formed on a glass substrate having a long side of 66 mm, a short side of 24 mm, and a thickness of 1.1 mm, and 200 μL of the composition for forming a water trapping body (J-1) was applied to the oyster. Then, it hardened | cured by UV irradiation described in the hardening conditions of Table 2 using the high pressure mercury lamp, and the water trapping body was formed.

[Examples 12-15]

Each water capture body was formed in the same manner as in Example 11 except that the composition for forming water trapping bodies shown in Table 2 was used.

Example 16 and Comparative Examples 3 to 4

Except having hardened | cured by the heating described in the hardening conditions of Table 2 using the composition for water trapping body formation shown in following Table 2, it operated like Example 11, and formed each water trapping body.

<Evaluation>

The film-forming properties and storage stability of each of the prepared water trapping body-forming compositions, and the hygroscopicity, heat resistance and adhesion of the formed water trapping body were evaluated according to the following methods. The evaluation result is shown according to the said Table 1 and Table 2.

[Film formation]

The external appearance was observed with the naked eye about the water trapping body formed with each composition for water trapping body formation. Under the present circumstances, when a crack and unevenness | corrugation were not confirmed, it evaluated as "good" "A", and when at least one of a crack or unevenness | corrugation was confirmed, it was evaluated as defective "B".

[Storage stability]

Each composition for water trapping body formation immediately after preparation was added to a transparent glass container, and it sealed and stored. After adding this composition to the said glass container, the elapsed time from the time when fluidity was not confirmed to the said composition was measured, and this elapsed time was made into storage stability. Confirmation of fluidity was performed by inclining the said glass container and observing the composition state at that time visually. When elapsed time is four days or more, storage stability can be evaluated as favorable.

Hygroscopicity

The mass of each of the formed water trapping bodies was precisely weighed, and the water trapping body was exposed to the air, and the change in mass over time was measured. The mass at the point of time when the change disappeared over time was rearranged, and the mass increase rate was expressed as a percentage as the water absorption rate (mass%), and the hygroscopicity index was used. Under the present circumstances, when water absorption is 1 mass% or more, hygroscopicity is favorable, and when it is less than 1 mass%, it can evaluate as defect.

[Heat resistance]

An appropriate amount of each composition for forming water trapping bodies is placed in the sample tube, and a water trapping agent having a film thickness of 2 mm is formed on the bottom of the sample tube under the same conditions as the curing conditions of the above-mentioned <Formation of water trapping body>. did. Subsequently, the formed water trapping body is exposed to the atmosphere and sufficiently hygroscopic. did. Then, the state of the water trapping body after 336 hours passed was observed. Under the present circumstances, when a change was not confirmed by the water trapping body, heat resistance was good "A", and when a water trapping body extended downward and deformation | transformation was confirmed, it evaluated as defect "B".

[Adhesion]

About each said water trapping body formed, when adhesiveness was not peeled from the said glass substrate in air | atmosphere, it evaluated as good "A", and when peeling, bad "B".

As is clear from the results of Table 1 and Table 2, in the comparative example, the composition for forming a water trapping body and the water trapping body of the examples may have any of film forming properties, storage stability, hygroscopicity, heat resistance and adhesion. At least one of the above characteristics was defective.

The present invention can provide a water trapping agent capable of forming a water trapping body excellent in hygroscopicity, heat resistance and adhesion while being excellent in film formation and storage stability of the composition for forming a water trapping body. Therefore, the present invention can provide a composition for forming a water trapping body capable of forming a water trapping body having excellent heat resistance, adhesion, and the like, a water trapping body formed from the composition, and an electronic device including the water trapping body. It can be used suitably for electronic devices, such as organic electroluminescent element which requires long lifetime.

10: organic EL layer
20: structure
22: substrate
24: bag cap
26: adhesive
30, 40: water trap
100, 200: organic EL device

Claims (13)

The water trapping agent which consists of a compound (a) containing the structure represented by following formula (1):

(In formula (1), R <^1> is -O-, -S-,-between the (r1) acyl group, (r2) the C1-C30 hydrocarbon group, or (r3) the carbon-carbon bond of this hydrocarbon group.) A group comprising at least one group selected from the group consisting of CO-, -CS-, -NH-, -SO- and -SO _2- , or (r4) these (r1), (r2) and (r3) A group in which a part of the hydrogen atom having the substituent is substituted with a hydroxy group, a halogen atom or a cyano group, M ¹ is a boron atom, an aluminum atom, a gallium atom, an indium atom or a tarium atom, X is an organic ligand; n Is an integer of 1 to 20; when n is 2 or more, a plurality of R ¹ , X and M ¹ may be the same or different, respectively; * ¹ and * ² represent a binding site to another site, or Or combined with each other). The method of claim 1,
The coordination atom of the said organic ligand is at least 1 sort (s) chosen from the group which consists of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. 3. The method of claim 2,
The water trapping agent, wherein the organic ligand is at least one member selected from the group consisting of a compound having a heterocycle, a compound having an ester group, a compound having an amide group, and a compound having an amino group. The method of claim 3,
M ¹ is an aluminum atom, water trapping agent. 5. The method of claim 4,
A water trapping agent wherein R ¹ is an acyl group. The method of claim 5,
A water trapping agent wherein R ¹ is represented by the following Formula (2):

(In formula (2), R <^2> , R <^3> and R <^4> respectively independently represents a C1-C12 monovalent hydrocarbon group or a part of the hydrogen atom which this hydrocarbon group has a hydroxyl group, a halogen atom, or a cyano group. Q is an integer of 0 to 6, and * ³ represents a bonding site with an oxygen atom. The method according to claim 6,
The water trapping agent in which the said compound (a) contains the cyclic aluminoxane compound of reduced water 6. The method of claim 7, wherein
A water trapping agent, wherein the cyclic aluminoxane compound is a compound obtained by reacting the organic ligand with cyclic aluminoxane of reduced water 6. The water trapping agent formation composition containing the water trapping agent in any one of Claims 1-8, and the compound which has a polymeric group. 10. The method of claim 9,
The composition for forming water trapping bodies, wherein the polymerizable group is a cyclic ether group. A water trapping agent-forming composition comprising the water trapping agent according to any one of claims 1 to 8 and inorganic particles. The water trapping body formed from the composition for water trapping body formation of Claim 9. An electronic device comprising the water trapping material according to claim 12.

Images