JP2015122297A - Organic el element and moisture-trapping film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element capable of efficiently eliminating the effect of moisture on an organic EL layer.SOLUTION: An organic EL element 100 includes a substrate 10, an organic EL layer 40 formed on the substrate, and a sealing member 30 and also includes, in a sealed space of the organic EL element, a moisture-trapping film formed using a composition for forming a moisture-trapping film, which contains (A) a compound having a hydrolyzable structure and (B) at least one compound selected from an acid generator and a base generator.

Description

  The present invention relates to an organic EL element and a moisture capturing film.

  One of electronic devices that has been actively developed in recent years is an organic electroluminescence (EL) element. An organic EL element is a simple device having a laminated structure (organic EL layer) composed of an anode / organic light emitting layer / cathode as a basic structure, and is a light emitting element capable of obtaining bright light emission. It has a problem that it is easy to receive.

  In other words, as the driving period becomes longer, the organic EL element is affected by moisture that has entered the element, and there is concern about the formation of so-called dark spots, and the light emission characteristics such as luminance and light emission efficiency gradually decrease. Have concerns.

  Therefore, the organic EL element must have a sealing structure that blocks the organic light emitting layer from the atmosphere, and a metal or glass sealing member and a substrate on which the organic EL layer is formed are combined with an appropriate sealing material. A technique for sealing the organic EL layer in a sealing space formed between the substrate and the sealing member has been studied.

  And in an organic EL element, in order to exclude the influence of a water | moisture content more effectively, the technique using a desiccant is examined. For example, a technique is known in which a desiccant such as phosphorous pentoxide particles is disposed in a position separated from the anode and the cathode in the above-described sealed space where the organic light emitting layer is sealed to maintain a low humidity environment. An organic EL element having such a drying means has been proposed (see, for example, Patent Document 1).

Japanese Patent Laid-Open No. 03-261091

  The organic EL element is required to be used in a sealed state in which moisture in the element is removed and moisture is prevented from entering the element from the outside. However, in the prior art in which the phosphorous pentoxide particles known as a desiccant are used as a desiccant, and the desiccant is disposed so as to be separated from the anode and the cathode sandwiching the organic light emitting layer in the sealed space, It was difficult to sufficiently eliminate the influence of moisture on the organic light emitting layer.

  Therefore, in the organic EL element, the moisture capturing technology that can efficiently remove the moisture in the sealed space where the organic EL layer is sealed, and the corresponding influence of moisture on the organic EL layer are efficiently performed. There is a need for organic EL elements that can be eliminated.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an organic EL element and a moisture capturing film that can efficiently eliminate the influence of moisture on the organic EL layer.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by an organic EL element and a moisture trapping film having the following configuration, and have completed the present invention.

For example, the present invention relates to the following [1] to [7].
[1] An organic EL element having a substrate, an organic EL layer formed on the substrate, and a sealing member, wherein (A) a structure that can be hydrolyzed in a sealing space of the organic EL element An organic EL device having a moisture-trapping film formed using a moisture-trapping film-forming composition comprising a compound having a water content and (B) at least one compound selected from an acid generator and a base generator.

  [2] The compound (A) is at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), carvone At least selected from the group consisting of acid anhydride (A2), and at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) The organic EL device according to [1], wherein the organic EL device is one type and the compound (B) is an acid generator.

[In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or a carbon number. 1 to 18 organic groups, and two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18, and * represents a bonding position; in formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each ⁸ is independently an organic group having 3 to 10 carbon atoms. ]

[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, 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 is 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 number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca P is an integer of 0-6; r is an integer of 0-2; s is an integer of 1-30. ]

  [3] The compound (A) is at least one selected from the carboxylic acid anhydride (A2), the compound represented by the formula (A3-1), and the compound represented by the formula (A3-2). [1] The organic EL device of [1], wherein the compound (B) is at least one selected from the group consisting of the compound (A3).

[4] The organic EL device according to any one of [1] to [3], wherein the composition for forming a moisture capturing film further contains (C) a polymerizable compound.
[5] The organic EL layer according to any one of [1] to [4], wherein the organic EL layer has a structure in which an organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other. element.

[6] The organic EL element according to any one of [1] to [5], wherein the moisture capturing film is disposed so as to be separated from the sealing member.
[7] It is formed using a composition for forming a moisture trapping film, comprising (A) a compound having a hydrolyzable structure and (B) at least one compound selected from an acid generator and a base generator. A moisture trapping film disposed in a sealing space of an organic EL element having a substrate, an organic EL layer formed on the substrate, and a sealing member.

  ADVANTAGE OF THE INVENTION According to this invention, the organic EL element which can exclude the influence of the water | moisture content to an organic electroluminescent layer efficiently, and the moisture capture film which can exclude the influence of the water | moisture content to an organic electroluminescent layer efficiently are provided. can do. Therefore, according to the present invention, it is possible to provide 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. Therefore, the organic EL element of the present invention can be suitably used for TVs and portable information devices that require high reliability.

FIG. 1 is a cross-sectional view schematically showing an example of the organic EL element of the present invention. FIG. 2 is a cross-sectional view schematically showing an example of the organic EL element of the present invention. FIG. 3 is a cross-sectional view schematically showing an example of the organic EL element of the present invention. FIG. 4 is a cross-sectional view schematically showing an example of the organic EL element of the present invention. FIG. 5 is a cross-sectional view schematically showing an example of the organic EL element of the present invention.

The organic EL device and the moisture capturing film of the present invention will be described.
[Organic EL device]
The organic EL element of the present invention is an organic EL element having a substrate, an organic EL layer formed on the substrate, and a sealing member used for sealing the organic EL layer. In the sealing space of an element, it has the moisture capture film formed using the composition for moisture capture film formation mentioned later.

<substrate>
As the substrate (device substrate) of the organic EL device, a substrate having excellent visible light transmittance and low oxygen transmittance and moisture transmittance is used, and examples thereof include a glass substrate and a transparent resin substrate. Examples of the constituent material of the substrate include glass such as alkali-free glass; polyester (eg, polyethylene terephthalate, polyethylene naphthalate), fluorene ring-modified polyester, polyolefin (eg, polyethylene, polypropylene), alicyclic polyolefin, polystyrene, Acetylcellulose, polyimide, fluorinated polyimide, polyamide, polyamideimide, polyetherimide, polyarylate, polyethersulfone, polysulfone, polyetheretherketone, polycarbonate, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, polyvinyl chloride, polychlorinated Examples thereof include transparent resins such as vinylidene, polyurethane, and (meth) acryloyl compounds. In addition, a board | substrate is not limited to the said illustration.

<Organic EL layer>
Although the details of the structure of the organic EL layer of the organic EL element are omitted, a structure in which an organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other, specifically, an anode facing each other A basic structure is a structure sandwiched between a cathode and a cathode (a laminated structure including an anode / organic light emitting layer / cathode), and various structures can be adopted as will be described later.

The organic light emitting layer contains a light emitting material that is an organic material, that is, an organic light emitting material. The organic light emitting material contained in the organic light emitting layer may be a low molecular organic light emitting material or a polymer organic light emitting material. For example, a material obtained by doping quinacridone or coumarin into a base material base such as Alq ₃ (tris (8-quinolinolato) aluminum), BeBq ₃ (bis (10-hydroxybenzo [h] quinolinate) beryllium) can be used. Moreover, when using the coating method of the organic luminescent material by the inkjet method, it is preferable that it is a polymeric organic luminescent material suitable for it. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, polyparaphenylene ethylene and derivatives thereof, poly 3 -Hexylthiophene (Poly 3-hexyl thiophene (P3HT)) and its derivatives, polyfluorene (Poly fluorene (PF)), its derivatives, etc. can be selected and used.

The anode and cathode of the organic EL layer are each made of a conductive material.
As the material for the anode of the organic EL layer, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide, or the like is selected.

  In the organic EL layer, a hole injection layer and / or an intermediate layer may be disposed between the anode and the organic light emitting layer. When the hole injection layer and the intermediate layer are disposed between the anode and the organic light emitting layer, the hole injection layer is disposed on the anode, the intermediate layer is disposed on the hole injection layer, and on the intermediate layer. An organic light emitting layer is disposed on the substrate. Further, the hole injection layer and the intermediate layer may be omitted as long as holes can be efficiently transported from the anode to the organic light emitting layer.

As a material for the cathode of the organic EL layer, for example, ITO, IZO, tin oxide, or the like can be selected. Further, for example, barium (Ba), barium oxide (BaO), aluminum (Al), an alloy containing Al, or the like can be selected.
In the organic EL layer, an electron injection layer made of, for example, barium (Ba), lithium fluoride (LiF), or the like may be disposed between the cathode and the organic light emitting layer.

<Sealing member>
As the sealing member, a member having low oxygen permeability and moisture permeability is used, and examples thereof include a member made of glass or resin. Examples of the constituent material of the sealing member include resins such as polyethylene terephthalate, polyethylene naphthalate, and polyimide, as well as the substrate, and other resins exemplified in the <Substrate> column. The sealing member is made of an inorganic material, for example, a substrate formed of an inorganic material such as a glass substrate such as a non-alkali glass substrate, or a material obtained by kneading an inorganic material and a resin. It is also possible to use a substrate in which an inorganic material is vapor-deposited or applied on a formed substrate, glass substrate or resin substrate.

  The sealing member is fixed to the substrate by a sealing material, for example. An adhesive resin material is used as the sealing material for the organic EL element, and a thermosetting or photocurable resin material can be selected as a constituent member. Examples of the thermosetting resin material include phenol resin, silicone resin, allyl ester, acrylic resin, epoxy resin, polyimide, and urethane resin. Examples of the photocurable resin material include silicone resin, acrylic resin, epoxy resin, polyimide, and urethane resin.

  The aspect which fixes a board | substrate and a sealing member using a sealing material is not specifically limited. For example, a sealing material may be formed on the periphery of the organic EL layer in the substrate to fix the sealing member to the substrate. In this case, the organic EL element has a hollow structure. Further, the gap space (hollow structure) in the organic EL element may be filled with a sealing material.

  For example, a structure including a substrate, a sealing material, and a sealing member fixed to the substrate with the sealing material allows the organic EL layer formed on the substrate to be stored in a sealing space formed by the structure. Thus, contact between the organic EL layer and the outside air can be blocked.

<Moisture capture film>
The moisture capturing film of the present invention is formed from a composition for forming a moisture capturing film described later. The moisture capturing film can efficiently remove moisture in the organic EL element, and can effectively eliminate the influence of moisture on the organic light emitting layer. In addition, the moisture trapping film hardly generates a decomposition product having high volatility such as a low molecular alcohol even in a state where moisture is trapped, and when used in an organic EL element, Generation of dark spots due to adhesion of the decomposition products can be suppressed.

  In the sealed space of the organic EL element, the arrangement location of the moisture capturing film is not particularly limited. For example, the moisture capturing film is disposed on the organic EL layer so as to be in surface contact with the organic EL layer (for example, so as to cover the surface of the organic EL layer on the sealing member side) and to be separated from the sealing member. It may be formed so as to be in surface contact with the side surface of the sealing material (for example, to cover the surface of the sealing material on the sealing space side).

The moisture capturing film may be supported or sandwiched by a support material.
A transparent resin substrate or the like can be used as the support material that supports the moisture capturing film and the pair of support materials that are sandwiched. Examples of the constituent material of the support material include transparent resins such as polyethylene terephthalate, polyethylene naphthalate, polyimide, and triacetylene cellulose, and other resins exemplified in the <Substrate> column.

  The moisture trapping film and the moisture trapping film supported or sandwiched by the support material can be placed in another sealed space on the organic EL layer using, for example, a known adhesive. Examples of the pressure-sensitive adhesive include a material that does not require the help of heat or a solvent and can be attached to another adherend with a very low pressure such as pressing with a finger. For example, as the pressure-sensitive adhesive, materials such as rubber, acrylic and silicone can be used.

  Further, when the moisture trapping film and the moisture trapping film supported or sandwiched by the support material are more firmly fixed on the organic EL layer, a curable adhesive can be used as the adhesive. Preferable curable adhesives include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, and thermosetting acrylic adhesives.

  In addition, since the composition for moisture capture film formation is excellent also in adhesiveness, when apply | coating the composition for moisture capture film formation on an organic EL layer and forming a moisture capture film, it is not necessary to use an adhesive. .

  In the moisture capturing film supported or sandwiched by the moisture capturing film or the supporting material, the moisture capturing film or the supporting material may be disposed so as to be in direct surface contact with the organic EL layer, and is disposed on the organic EL layer via the adhesive. It may be arranged. For example, in the case of a moisture capturing film sandwiched between a pair of support materials, one of the support materials may be in direct surface contact with the organic EL layer, and one of the support materials may be an organic EL layer via the adhesive. The structure arrange | positioned on a surface may be sufficient.

  Moisture trapping film or moisture trapping film supported or sandwiched by a support material is placed on the organic EL layer using an adhesive to prevent moisture trapping film from peeling from the organic EL layer, etc. The reliability of the film can be improved.

  The organic EL element of the present invention having the above structure can remove moisture in the sealed space in which the organic EL layer is housed by having the moisture capturing film of the present invention. And the moisture capture film of this invention can absorb a water | moisture content over a long period of time, and can suppress deterioration of the organic EL element resulting from a water | moisture content. That is, the moisture capturing film of the present invention can efficiently eliminate the influence of moisture on the organic light emitting layer of the organic EL element. Therefore, the organic EL element can constitute, for example, an organic EL lighting device or an organic EL display element having high reliability.

  As a method for forming a moisture capturing film, for example, Step 1 of forming a coating film on the organic EL layer formed on the substrate by using a composition for forming a moisture capturing film described later, the coating film is irradiated with radiation. And a method of forming by the step 2 of heating or irradiation and heating.

  Moreover, you may create an organic EL element using the moisture capture film formed previously. In the case of forming a moisture capturing film supported by a support material, for example, Step 1 ′ of forming a coating film on the supporting material using the composition for forming a moisture capturing film, the coating film is irradiated with radiation, and heated. Or a method of forming by step 2 ′ of irradiation and heating. In the case of forming a moisture capturing film sandwiched between a pair of supporting materials, for example, after the step 1 ′, the other supporting material is bonded onto the coating film before the step 2 ′. The moisture capturing film thus obtained is placed on, for example, an organic EL layer using an adhesive as necessary.

  The composition for forming a moisture trapping film can be applied onto an organic EL layer or a support material to be applied by, for example, a spin coater, roll coater, spray coater, bar coater, dispenser, or inkjet device.

  The radiation in Steps 2 and 2 ′ is not particularly limited as long as the hydrolysis reaction described below can proceed in the composition, and preferably the coating film can be cured, but visible light, ultraviolet light, far ultraviolet light, X-ray and Examples thereof include charged particle beams, and ultraviolet rays are preferable. When heating is performed in steps 2 and 2 ′, the heating temperature is preferably 30 to 200 ° C., more preferably 50 to 150 ° C .; the heating time is preferably 1 minute to 24 hours, and 10 minutes to 5 hours. Is more preferable.

For the radiation of the composition in Steps 2 and 2 ′, known methods and conditions can be used. For example, a high-pressure mercury lamp is used and ultraviolet irradiation (eg, 500 to 15000 mJ / cm ² ) is performed. Can do.

  Although the film thickness of a moisture capture film is not specifically limited, For example, it is 1-500 micrometers, Preferably it is 5-200 micrometers, More preferably, it is 5-100 micrometers. The film thickness of the film can be measured, for example, with a depth gauge 547-251 (manufactured by Mitutoyo Corporation).

The moisture capturing film is excellent in visible light transmittance even in a humid heat environment. For this reason, even if it arrange | positions in the sealing space of an organic EL element, there is no possibility that the light emission characteristic of an organic EL element may be inhibited.
Since the moisture capturing film of the present invention is formed from a composition for forming a moisture capturing film described later, the organic EL layer is sealed by disposing the moisture capturing film in the sealing space of the organic EL element. Water in the sealed space can be removed efficiently.

<< Specific examples of organic EL elements >>
Several examples of embodiments of the organic EL element of the present invention will be described with reference to the drawings.
An organic EL element 100 shown in FIG. 1 includes a substrate 10, a sealing material 20, and a sealing member 30 fixed to the substrate 10 by the sealing material 20. In the formed sealing space, the organic EL layer 40 formed on the substrate 10 and the moisture capturing film 50 formed on the organic EL layer 40 are provided. A gap such as between 50 and the sealing member 30 is formed. That is, the organic EL element 100 is in surface contact with the organic EL layer 40 (so as to cover the surface of the organic EL layer 40 on the sealing member 30 side) and is separated from the sealing member 30 in the sealing space. The moisture capturing film 50 is disposed on the organic EL layer 40.

  It is also possible to fill the gaps in the sealed space with a sealing material so that no gaps are formed in the sealed space. In the organic EL element 200 shown in FIG. 2, a sealing material 201 corresponding to the sealing material 20 of the organic EL element 100 shown in FIG. 1 is provided over the entire area between the substrate 10 and the sealing member 30. The sealing material 201 fixes the substrate 10 and the sealing member 30 and fills the sealing space formed between the substrate 10 and the sealing member 30 without a gap. With such a structure, the sealing material 201 can protect the organic EL layer 40 and the moisture capturing film 50 formed on the substrate 10. As a result, the reliability performance of the organic EL element 200 can be improved.

  In the organic EL elements 100 and 200 shown in FIGS. 1 and 2, the moisture capturing film 50 is provided in direct contact with the organic EL layer 40, but the present invention is not limited to such a structure. , May be provided via an adhesive. In addition, for example, it is possible to support or sandwich the moisture capturing film with an appropriate support material and arrange the moisture capturing film on the organic EL layer together with the support material. 3 and 4 show organic EL elements 300 and 400 in which the arrangement of the moisture capturing film is changed to such a form in FIGS. 1 and 2, respectively.

  In the organic EL elements 300 and 400 shown in FIGS. 3 and 4, a moisture capturing film 501 sandwiched between a pair of support members 502 and 503 is disposed on the organic EL layer 40 via an adhesive (not shown). That is, the support material 503 and the organic EL layer 40 are bonded together with an adhesive. In the organic EL elements 300 and 400 shown in FIGS. 3 and 4, the organic EL element 40 is in surface contact with the organic EL layer 40 on the organic EL layer 40 in the sealing space between the organic EL layer 40 and the sealing member 30. In addition, a moisture capturing film 501 sandwiched between a pair of support members 502 and 503 is disposed so as to be separated from the sealing member 30.

  Further, in the organic EL element 400 illustrated in FIG. 4, the sealing material 201 corresponding to the sealing material 20 of the organic EL element 300 illustrated in FIG. 3 is provided in the entire region between the substrate 10 and the sealing member 30. . The sealing material 201 fixes the substrate 10 and the sealing member 30 and fills the sealing space formed between the substrate 10 and the sealing member 30 without a gap.

  An organic EL element 101 shown in FIG. 5 includes a substrate 10, a sealing material 20, and a sealing member 30 fixed to the substrate 10 by the sealing material 20. The organic EL element 101 includes the substrate 10, the sealing material 20, and the sealing member 30. In the formed sealing space, the organic EL layer 40 formed on the substrate 10 and the moisture capturing film 510 formed so as to be in surface contact with the side surface of the sealing material 20 are provided. Here, the sealing material 20 is formed on the periphery of the organic EL layer 40 in the substrate 10.

[Moisture capture film forming composition]
The composition for forming a moisture capturing film used in the present invention contains a compound (A) having a hydrolyzable structure and at least one compound (B) selected from an acid generator and a base generator. Moreover, it is preferable that the said composition further contains a polymeric compound (C).

  In the following description, the compound (A) and the compound (B) are also referred to as a water trapping agent (A) and an acid / base generator (B), respectively, and the water trapping agent (A) and the acid / base generator (B). ) And the polymerizable compound (C) are also referred to as a component (A), a component (B), and a component (C), respectively. The same applies to other examples unless otherwise specified.

[Moisture capture agent (A)]
The moisture trapping agent (A) is a compound having a structure that can be hydrolyzed in the presence of an acid or a base, for example. As the moisture capturing agent (A), for example, at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), Carboxylic anhydride (A2), and at least one compound (A3) selected from a compound represented by formula (A3-1) and a compound represented by formula (A3-2) can be mentioned. Each of these compounds (A1) to (A3) may be used alone or in combination of two or more. In the following description, the compounds (A1) to (A3) are also referred to as moisture trapping agents (A1) to (A3), respectively.

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

In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms; R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or 1 carbon atom. -18 organic groups; two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded together to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18; * indicates a bonding position. In formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; R ⁸ is each independently an organic group having 3 to 10 carbon atoms.

In addition, in description of each formula which concerns on a moisture capture agent (A1), unless otherwise mentioned,
Examples of the “organic group having 1 to 18 carbon atoms” include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, 2-ethylhexyl. , Decyl, dodecyl, octadecyl or the like linear or branched alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms; cycloalkyl having 3 to 12 carbon atoms such as cyclohexyl or methylcyclohexyl A cycloalkyl group-substituted alkyl group having 4 to 18 carbon atoms such as cyclohexylmethyl or cyclohexylethyl; a phenyl group; an aralkyl group having 7 to 18 carbon atoms such as a phenyl-substituted alkyl group (eg, benzyl group or phenethyl group); A group in which a part of these groups is substituted with an oxygen atom (hereinafter also referred to as “oxygen atom substituent”); ; Vinyl group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, a glycidyl group; include carboxyl group, also can be a group represented by the following formula G1 to G7;
Examples of the “organic group having 3 to 10 carbon atoms” include carbon atoms having at least one group selected from “vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group and glycidyl group”. The organic group of 3-10 is mentioned, Moreover, group represented by the following formula g1-g7 can also be mentioned.

In the above formulas g1 to g7, * represents a bonding position.

  Examples of the oxygen atom substituent include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl; alkanoyloxyalkyl groups such as acetoxymethyl and acetoxyethyl; aryloxyalkyl groups such as phenoxymethyl and phenoxyethyl; An alkoxy group such as methoxy; an aryloxy group such as phenoxy; and a hydroxyalkyl group such as hydroxymethyl.

In formula (A1-1), the total number of carbon atoms of the groups represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ (when n is 0, it is represented by R ^{2 to} R ⁵ . The total number of carbon atoms of the groups to be formed is preferably 0 to 18, more preferably 0 to 12, from the viewpoint of water absorption ability and solubility.

Further, two or more groups selected from R ³ , R ⁴ and R ⁷ (when n = 0, R ³ and R ⁴ ) are bonded to each other, together with the carbon atom to which they are directly bonded. The ring structure may be formed. Examples of the cyclic structure include a cyclohexane ring and a cyclopentane ring.

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

In formula (A1-1), R ^{6 to} R ⁷ each independently represent a hydrogen atom, a hydroxyl group, the above-described alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 4 to 18 carbon atoms. A cycloalkyl group-substituted alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, an oxygen atom substituent, a vinyl group, an allyl group, a (meth) acryloyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a carboxyl group, It is preferably a group represented by the above formulas g1 to g7, and more preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the above formulas g1 to g2.

R ^{1 to} R ⁷ are preferably the above atoms or groups from the viewpoint of water absorption ability as a moisture trapping agent and compatibility with other components.
In formula (A1-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R ⁶ and R ⁷ may be the same or different.
In formula (A1-2), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁸ is preferably independently a group represented by the above formulas g1 to g7.

<< Compound having a structural moiety represented by the formula (A1-1) >>
As a compound which has a structure part represented by a formula (A1-1), the compound represented by a following formula is mentioned, for example. Specific examples of this compound include compounds represented by the following formula (A1-i), formula (A1-ii), and formula (A1-iii).

In the formula, A is a structural moiety represented by the formula (A1-1); Y is a hydroxyl group-containing compound (a3) described later having p (p ≧ 2) hydroxyl groups in one molecule; Residues excluding m (2 ≦ m ≦ p) hydroxyl groups; m is an integer of 2 to p.

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

Orthoester (a1)
The ortho ester (a1) is a compound represented by the formula (a1).

In the formula (a1), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; each of three Ras is independently an organic group having 1 to 18 carbon atoms. The organic group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a substituted alkyl group having 4 to 18 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.

Examples of the orthoester (a1) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, orthobutyric acid. Ethyl is mentioned. Among these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate are preferable.
Orthoester (a1) may be used individually by 1 type, and may use 2 or more types together.

Polyhydric alcohol (a2)
As a polyhydric alcohol (a2), the compound which has 2 or more of hydroxyl groups in 1 molecule is mentioned, for example, The compound represented by a formula (a2-1) is preferable. Specific examples include α-glycol having two hydroxyl groups in one molecule and a compound having two or more hydroxyl groups in one molecule other than α-glycol.

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

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

  α-glycol in which n is 0 is preferred. α-Glycol has two adjacent hydroxyl groups. Therefore, the reaction between the ortho ester and α-glycol proceeds efficiently, which is suitable for the production of a moisture trapping agent.

  Examples of α-glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dodecanediol, 1,2- Hydrolyzate of dihydroxycyclohexane, pinacol, long chain alkyl monoepoxide; fatty acid monoglyceride (α form) such as glycerin monoacetate (α form), glycerin monostearate (α form); 3-ethoxypropane-1,2-diol , 3-phenoxypropane-1,2-diol. Among these, ethylene glycol, 1,2-propylene glycol, and 1,2-hexanediol are preferable.

  A compound in which n is 1 is particularly preferred. The said compound has two or three or more hydroxyl groups which adjoined like the alpha-glycol mentioned above. Therefore, the reaction between the ortho ester and the compound proceeds efficiently, which is suitable for the production of a moisture trapping agent.

  Examples of the compound in which n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2- Ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propane Diol, (2-allyloxymethyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, glycerin, 2-phenoxypropane-1,3-diol Diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylolpropylene Acid, dimethylolbutanoic acid, 2-ethyl-1,3-octanediol, 1,3-dihydroxycyclohexane; fatty acid monoglycerides (β form) such as glycerin monoacetate (β form) and glycerin monostearate (β form) Is mentioned. Among these, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexane Diol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, (2-allyloxy Particularly preferred are methyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, and glycerin.

Hydroxyl-containing compound (a3)
The hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule.
When the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, from the polyhydric alcohol (a2) such as a compound represented by the formula (a2-1) A hydroxyl group-containing compound (a3) can also be selected and used. In that case, it is preferable that the compound selected as the hydroxyl group-containing compound (a3) is selected from compounds other than the compound selected as the polyhydric alcohol (a2).

  Examples of the hydroxyl group-containing compound (a3) include a compound having 2 hydroxyl groups in one molecule and a compound having 3 or more, preferably 3 to 40 hydroxyl groups in one molecule.

  Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, and 3-methyl. 1,5-pentanediol, 1,4-dimethylolcyclohexane, tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate [this is hydroxy Corresponds to an ester of pivalic acid and neopentyl glycol], bisphenol A, bisphenol F, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9-bis (1 , 1-Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxa Pyro [5,5] undecane, diethylene glycol, triethylene glycol, tetra or higher polyethylene glycol, dipropylene glycol, tripropylene glycol, tetra or higher polypropylene glycol, hydroxyl groups at both ends formed by copolymerization of ethylene oxide and propylene oxide A linear polyester having hydroxyl groups at both ends, such as a polycaprolactone diol, polycarbonate diol, and a diepoxide carboxylic acid adduct.

  Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxy). Ethyl) isocyanurate, gluconic acid, polymers containing 3 or more hydroxyl groups (polyesters containing 3 or more hydroxyl groups, polyethers, acrylic polymers, ketone resins, phenol resins, epoxy resins, urethane resins, polyvinyl acetates) Saponified polyvinyl alcohol, natural sugars such as glucose, etc.).

  As the hydroxyl group-containing compound (a3), a compound having a molecular weight in the range of 90 to 100,000, particularly 90 to 5,000 is preferable. The hydroxyl group-containing compound (a3) is preferably a compound having a hydroxyl value in the range of 20 to 1850 mgKOH / g, particularly 40 to 1650 mgKOH / g.

Reaction ratio Orthoester (a1), polyhydric alcohol (a2), and hydroxyl group-containing compound (a3) are reacted to produce a water scavenger (A1). In this case, orthoester (a1) and polyhydric alcohol (a2) are produced. ) And the hydroxyl group-containing compound (a3) are not particularly limited.

  For example, the amount of the ortho ester (a1) is 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 with respect to 1 mol equivalent of the hydroxyl group in the hydroxyl group-containing compound (a3). The ratio of the polyhydric alcohol (a2) in the range of 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol. It is appropriate to use it from the viewpoint of easy control of the molecular weight. When the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2), the compound selected as the hydroxyl group-containing compound (a3) is a compound other than the compound selected as the polyhydric alcohol (a2). Selected.

  The moisture trapping agent (A1) can be obtained by subjecting three components of an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) to a condensation reaction. For example, the above-mentioned three components are usually used in the presence of an organic solvent and an acid catalyst such as formic acid, usually at room temperature to 250 ° C., preferably 70 to 200 ° C. for 1 hour to 20 hours. It can manufacture suitably by carrying out a condensation reaction by heating to the extent. Moreover, you may convert the group which the compound obtained by the above method has into another group by a well-known method. For the synthesis method, for example, International Publication No. 01/021611 pamphlet can be referred to.

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

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

In formula (A1-i), Y ¹ is an m-valent residue obtained by removing m (2 ≦ m ≦ p) hydroxyl groups from a compound having p (p = 2 to 6) hydroxyl groups in one molecule. It is. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound is synthesized by using, for example, an orthoester of formula (a1), a polyhydric alcohol of formula (a2-1), and a compound having 2 to 6 hydroxyl groups in one molecule as raw materials. Can do.

In formula (A1-ii), Y ² is a divalent residue obtained by removing two hydroxyl groups from a compound having two hydroxyl groups in one molecule. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound can be synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a compound having two hydroxyl groups in one molecule as raw materials.

In formula (A1-iii), Y ³ is a tetravalent residue obtained by removing four hydroxyl groups from a compound having four hydroxyl groups in one molecule. R ¹ to R ⁷ and n have the same meanings as R ¹ to R ⁷ and n in formula (A1-1). The above compound can be synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a compound having four hydroxyl groups in one molecule as raw materials.

Specific examples of the compound represented by the formula (A1-2) Specific examples of the compound represented by the formula (A1-2) include compounds represented by the following formula.

<Moisture capture agent (A2)>
The moisture trapping agent (A2) is a carboxylic acid anhydride, and examples thereof include monocarboxylic acid anhydrides, dicarboxylic acid anhydrides, and tetracarboxylic dianhydrides. The moisture scavenger (A2) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.

<Anhydride of monocarboxylic acid>
Examples of monocarboxylic acid anhydrides include trifluoroacetic anhydride, benzoic anhydride, isatoic anhydride, isopentanoic anhydride, isobutyric anhydride, n-valeric anhydride, crotonic anhydride, and the like. . The carbon number of the monocarboxylic acid anhydride is preferably 4 to 20, more preferably 4 to 14, from the viewpoint of the volatility of the carboxylic acid that can be generated by hydrolysis.
Monocarboxylic acid anhydrides may be used alone or in combination of two or more.

<Dicarboxylic anhydride>
As the dicarboxylic acid anhydride, a compound represented by the formula (A2-1) can be given.

In formula (A2-1), Ra is a divalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a “aromatic group directly Or a non-condensed polycyclic aromatic group connected to each other by a bridging member (eg, —O—, —CO—, —S—, —SO ₂ —, an alkylene group, —C (CF ₃ ) ₂ —) ” A divalent group selected from: The carbon number of Ra is usually 1-30, but preferably 4-30, more preferably 6-18, from the viewpoint of the volatility of the dicarboxylic acid that can be generated by hydrolysis.

Examples of the dicarboxylic acid anhydride include aliphatic dicarboxylic acid anhydrides, alicyclic dicarboxylic acid anhydrides, and aromatic dicarboxylic acid anhydrides.
Aliphatic dicarboxylic acid anhydrides include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other aliphatic saturated dicarboxylic acid anhydrides; maleic acid, fumaric acid And anhydrides of aliphatic unsaturated dicarboxylic acids such as itaconic acid, mesaconic acid and citraconic acid.

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

An aromatic dicarboxylic acid anhydride refers to a dicarboxylic acid anhydride of an organic compound in which at least two carboxyl groups are bonded to an aromatic ring. Examples of the aromatic dicarboxylic acid anhydride include phthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 2,3-dicarboxyphenyl phenyl ether, 3,4-dicarboxyphenyl phenyl ether, 2,3-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid, 2,3-dicarboxyphenylphenylsulfone, 3,4-dicarboxyphenylphenylsulfone, 2,3-dicarboxyphenylphenylsulfide, 3,4- Dicarboxyphenyl phenyl sulfide, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,2-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid, 1,9- Anthracene dicarboxylic acid, etc. Anhydrides of aromatic dicarboxylic acids.
A dicarboxylic acid anhydride may be used individually by 1 type, and may use 2 or more types together.

<< tetracarboxylic dianhydride >>
As the tetracarboxylic dianhydride, a compound represented by the formula (A2-2) can be given.

In the formula (A2-2), Rb is a tetravalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a “aromatic group directly Or a non-condensed polycyclic aromatic group connected to each other by a bridging member (eg, —O—, —CO—, —S—, —SO ₂ —, an alkylene group, —C (CF ₃ ) ₂ —) ” A tetravalent group selected from The carbon number of Rb is usually 4 to 100, but preferably 4 to 30 and more preferably 4 to 18 from the viewpoint of the volatility of the tetracarboxylic acid that can be generated by hydrolysis.

Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides.
Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (Tetrahydro-2,5-dioxo-3-furani ) -Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-) 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, -(2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride, compounds represented by formulas (T-1) and (T-2).

In formula (T-1) and formula (T-2), R ¹ and R ³ are divalent organic groups having an aromatic ring; R ² and R ⁴ are a hydrogen atom or an alkyl group, R ² and R ⁴ present may be the same or different.

  An aromatic tetracarboxylic dianhydride refers to a tetracarboxylic anhydride of an organic compound in which at least four carboxyl groups are bonded to an aromatic ring. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and 3,3 ′, 4,4′-diphenyl sulfone. Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′ , 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydrous 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4 , 4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol bis (anhydro trimellitate), propylene glycol bis (anhydro trimellitate) 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate) ), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6-bis (3,4- Dicarboxyphenyl) pyridine, and compounds represented by the following formulas (T-3-1) to (T-3-4).

A tetracarboxylic dianhydride may be used individually by 1 type, and may use 2 or more types together.

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

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

In the formulas (A3-1) and (A3-2), R ¹ is at least 1 selected from “(meth) acryloyl group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, mercapto group and isocyanate group”. An organic group having one 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 formulas (A3-1) and (A3-2), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 3 to 3 carbon atoms which may have a substituent. 12 cycloalkyl groups, optionally substituted aromatic hydrocarbon groups having 6 to 14 carbon atoms, (meth) acryloyloxy groups, glycidoxy groups, oxiranyl groups, oxetanyl groups, 3,4-epoxycyclohexyl groups, Or a mercapto group.

  In the formulas (A3-1) and (A3-2), r is an integer of 0 to 2; p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3. preferable. s is an integer of 1-30, the integer of 1-20 is preferable, and the integer of 1-10 is more preferable.

When there are a plurality of groups represented by — (CH ₂ ) _p —R ^2, they may be the same or different. When there are a plurality of groups represented by —OR ^1, they may be the same or different.

As said organic group in R < ¹ > in Formula (A3-1) and (A3-2), group represented by a following formula is mentioned, for example. In the following formula, * represents a bonding 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.

The alkyl group for R ¹ in formulas (A3-1) and (A3-2) may be linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl; and cycloalkyl groups include, for example, cyclohexyl.

The alkyl group for R ² in formulas (A3-1) and (A3-2) may be either linear or branched. Carbon number of the said alkyl group is 1-20, Preferably it is 1-10, More preferably, it is 1-6. 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. As a cycloalkyl group in R < ² > in Formula (A3-1) and (A3-2), a cycloheptyl group and a cyclooctyl group are mentioned, for example.

Examples of the aromatic hydrocarbon group for R ² in formulas (A3-1) and (A3-2) include monocyclic to tricyclic aromatic hydrocarbon groups, specifically, a phenyl group , Tolyl group, naphthyl group, anthryl group, and phenanthryl group. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferable, and a phenyl group is more preferable.

The alkyl group, cycloalkyl group and aromatic hydrocarbon group in R ² in the formulas (A3-1) and (A3-2) may have a substituent, and examples of the substituent include a halogen atom, Examples include 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.

R ² in the formulas (A3-1) and (A3-2) is preferably an alkyl group having 1 to 6 carbon atoms, a halogen-substituted alkyl group, a phenyl group, a (meth) acryloyloxy group, or a glycidoxy group. In addition, when ^two or more R < ² > exists in the same molecule, they may be same or different.

Specific examples of the compound (A3) include silane compounds in which X is a silicon atom.
In compound (A3-1),
Examples of the silane compound in which r is 0 and s is 1 include alkoxysilane compounds having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane; and 6 to 6 carbon atoms such as diphenyldimethoxysilane. 14 alkoxysilane compounds having two aromatic hydrocarbon groups; 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxy An silane having a (meth) acryloyloxy group and an alkyl group having 1 to 20 carbon atoms, such as silane, 3-acryloyloxypropylethyldimethoxysilane, and 3-acryloyloxypropylmethyldiethoxysilane. Coxysilane compounds; (meth) acryloyloxy groups such as 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldiethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldiethoxysilane, and carbon Alkoxysilane compounds having an aromatic hydrocarbon group of 6 to 14; 2 (meth) acryloyloxy groups such as 3,3′-dimethacryloyloxypropyldimethoxysilane and 3,3′-diaacryloyloxypropyldimethoxysilane One alkoxysilane compound; 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Alkoxysilane compounds having a glycidoxy group such as 3-glycidoxypropylethyldiethoxysilane and an alkyl group having 1 to 20 carbon atoms; 3-glycidoxypropylphenyldimethoxysilane, 3-glycidoxypropylphenyldiethoxy Examples thereof include alkoxysilane compounds having a glycidoxy group such as silane and an aromatic hydrocarbon group having 6 to 14 carbon atoms.

  Examples of the silane compound in which r is 1 and s is 1, include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri- alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as iso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, and decyltrimethoxysilane; and 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane Alkoxysilane compounds having one halogen-substituted alkyl group, alkoxysilane compounds having one C6-C14 aromatic hydrocarbon group such as phenyltrimethoxysilane, phenyltriethoxysilane, etc .; 3-methacryloyloxy Propyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltripropoxysilane And alkoxysilane compounds having one (meth) acryloyloxy group.

  Examples of the silane compound in which r is 2 and s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane. Is mentioned.

  As compound (A3-1), the compounds of formula (A3-i) and formula (A3-ii) shown below can be further exemplified. The compounds of the formula (A3-i) and the formula (A3-ii) are, as exemplified by the following formula, tetraethoxysilane, a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group, etc. ) Can be obtained by reacting in the presence of an alkali.

As compound (A3-1), the compounds of formula (A3-iii) and formula (A3-iv) shown below can be further exemplified. The compound of (A3-iii) and the formula (A3-iv) has a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group) as shown in the following formula. Etc.) can be obtained by reacting in the presence of an alkali.

Examples of the compound (A3-1) further include a compound represented by the formula (A3-v).

As the compound (A3-2),
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.
Moreover, as what can be purchased with the commercial item of a compound (A3), OXT-191 (made by Toagosei), X-22-3000T (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned, for example.

<Description of effects>
The effects of the moisture capturing film forming composition used in the present invention will be described below.
When the composition for forming a moisture capturing film used in the present invention is heated and / or irradiated with light, an acid or a base is formed from the acid / base generator (B). This acid or base accelerates the hydrolysis reaction of the moisture scavenger (A) based on the water present in the system in which the composition is used, 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 moisture trapping agent (A) is less likely to deteriorate the performance of the organic EL device as described later.

  For this reason, in this invention, when forming a moisture capture film in an organic EL element using the said composition, the water | moisture content in an element can be removed with high efficiency. In addition, it is considered that a part of the moisture trapping agent (A) or a structural portion derived therefrom remains without being decomposed in the moisture trapping film formed from the above composition. For this reason, moisture in the element can be absorbed over a long period of time after the formation, and deterioration of the characteristics of the organic EL element due to moisture can be suppressed.

  In general, the decomposition product is dispersed in the organic EL element by volatilization or the like, and reaches the organic EL layer that becomes the light emitting layer of the organic EL element to be contaminated and generate a dark spot. There is a concern of degrading the performance of the EL element. However, in this invention, since the hydrolysis product produced | generated from a moisture capture agent (A) is equipped with moderate molecular weight, volatilization etc. are suppressed and it can remain in a moisture capture film. As the hydrolysis product has a larger molecular size, it tends to stay in the moisture trapping film. Therefore, a compound having a relatively large molecular weight is preferable as the moisture trapping agent (A).

  The moisture trapping agent (A) used in the present invention hardly generates a highly volatile hydrolysis product such as a low molecular alcohol even when moisture is trapped. For example, adhesion of the hydrolysis product Thus, even when used in an organic EL element that easily generates dark spots, it is possible to suppress the generation of dark spots due to the adhesion of the decomposition products to the organic EL layer.

An example of the hydrolysis reaction of the moisture trapping agent (A) is shown below.
For example, the hydrolysis reaction of the water capturing agent having the structural site of formula (i-1) and the water capturing agent having the structural site of formula (i-2), which are examples of the water capturing agent (A1), is as follows. A chemical reaction formula can be shown. In the following formula, * represents a bonding position. It is considered that an alcohol compound is generated as a hydrolysis product. These alcohol compounds are less volatile and have an appropriate molecular weight.

  For example, examples of the moisture scavenger (A2) are a monocarboxylic acid anhydride of formula (ii-1), a dicarboxylic acid anhydride of formula (ii-2), and a tetracarboxylic acid dianhydride of formula (ii-3) The following chemical reaction formula can be shown for the hydrolysis reaction of the product. It is considered that carboxylic acid compounds such as carboxylic acid (ii-1-1), dicarboxylic acid (ii-2-1) and tetracarboxylic acid (ii-3-1) are generated as hydrolysis products. These carboxylic acid compounds are difficult to volatilize and have an appropriate molecular weight.

For example, the following chemical reaction formula can be shown for the hydrolysis reaction of the compounds of formula (iii-1) and formula (iii-2), which is an example of the moisture trapping agent (A3). As a hydrolysis product, alcohol compound (iii-1-1) and metal hydroxide (iii-1-2), alcohol compound (iii-2-1) and metal hydroxide (iii-2-2) Generate. Unreacted R ¹ O in the metal hydroxide (iii-1-2) can react with water to further generate an alcohol compound (iii-1-1). Alcohol compounds (iii-1-1) and (iii-2-1) can react in the R ¹ group and remain in the moisture capture film. Metal hydroxides (iii-1-2) and (iii-2-2) can react in the R ² group and remain in the moisture capture film. Further, the metal hydroxides (iii-1-2) and (iii-2-2) are fixedly held in the moisture capturing film by the R ² group and scattered in the film, and the water is regenerated by the condensation reaction. Occurrence is prevented.

[Compound (B)]
The composition for forming a moisture capturing film used in the present invention contains at least one compound (B) selected from an acid generator and a base generator. Hereinafter, the acid generator and the base generator are also referred to as “acid generator (B1)” and “base generator (B2)”, respectively.

  When the composition used by this invention contains an acid generator (B1), at least 1 sort (s) chosen from a moisture capture agent (A1)-(A3) is used as a moisture capture agent (A). When the composition used by this invention contains a base generator (B2), at least 1 sort (s) chosen from a water capture agent (A2)-(A3) is used as a water capture agent (A).

  Examples of the acid generator (B1) include a radiation sensitive acid generator and a thermal acid generator, and a radiation sensitive acid generator is 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. The acidic active substance to be released acts as a catalyst when the above-described water trapping agent (A) is subjected to a hydrolysis reaction, for example. The basic active substance to be released acts as a catalyst when the above-described water capturing agents (A2) and (A3) are subjected to a hydrolysis reaction, for example.

  Examples of the radiation irradiated to decompose the radiation-sensitive acid generator or the radiation-sensitive base generator and generate the cation of the acidic active substance or the anion of the basic active substance include, for example, visible light, ultraviolet light, far ultraviolet light, Examples include X-rays and charged particle beams. 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 used in the present invention, when the component (B) is an acid generator (B1), the content thereof is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), More preferably, it is 0.5-10 mass parts. By setting the content of component (B) within the above range, for example, a composition having excellent radiation sensitivity can be obtained.

In the composition used in the present invention, when the component (B) is a base generator (B2), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A), More preferably, it is 1-10 mass parts. By setting the content of component (B) within the above range, for example, a composition having excellent radiation sensitivity can be obtained.
Each of the components (B1) and (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, and SbF ₆ ⁻ , BF ₄ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , and PF _{6. ^{-, P (Rf) n F}} (6-n) - (Rf is, for example, a perfluoroalkyl group having 1 to 8 carbon atoms; n is an integer of 1 to _{3), C n F 2n + 1} SO 3 - is (n For example, a salt composed of an anion such as 1 to 8), N (SO ₂ CF ₃ ) ₂ ⁻ , C (SO ₂ CF ₃ ) ₃ ⁻ or the like is used. Specifically, CPI-100P, CPI101A, CPI-200K, CPI-210S, etc. (above, manufactured by Sun Apro), Sun-Aid SI-150L, Sun-Aid SI-110L, Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (Above, manufactured by Sanshin Chemical Industry Co., Ltd.), CI series such as PI-2074 manufactured by Rhodia, CI2920 manufactured by Nippon Soda Co., Ltd. Examples include WPAG series and WPI series.

Among these acid generators (B1), in the cationic curing catalyst, B (C ₆ F ₅ ) ₄ ⁻ , P (Rf) _n F _(6-n) ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ and C (SO ₂ CF ₃ ) ₃ ^— are preferable, and the cation is preferably a sulfonium cation substituted with an alkyl group or an aryl group from the viewpoint of storage stability.

  Moreover, as an acid generator (B1), Unexamined-Japanese-Patent No. 2006-096742, Unexamined-Japanese-Patent No. 2006-282633, Unexamined-Japanese-Patent No. 2010-241733, Unexamined-Japanese-Patent No. 2012-153642, Unexamined-Japanese-Patent No. 2012-201611 Further, thermal acid generators described in JP 2013-100300 A, JP 2013-058411 A, JP 5505656 A, and the like can be given.

<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 Can be mentioned.

  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.

  As other examples of the radiation sensitive base generator, 2-nitrobenzylcyclohexyl carbamate, O-carbamoylhydroxyamide and O-carbamoylhydroxyamide are particularly preferable.

  Moreover, as a base generator (B2), international publication 2011/136704 pamphlet, Unexamined-Japanese-Patent No. 2012-193340, Unexamined-Japanese-Patent No. 2013-241548, Unexamined-Japanese-Patent No. 2013-241607, Unexamined-Japanese-Patent No. 2014-097930 Mention may also be made of thermal base generators described in Japanese Patent Publication No. 2012/026400 pamphlet, Japanese Patent No. 5406995.

[Polymerizable compound (C)]
It is preferable that the composition for forming a moisture capturing film used in the present invention further contains a polymerizable compound (C). When the composition used in the present invention contains the polymerizable compound (C), for example, the crosslinking reactivity can be enhanced. And the intensity | strength of the moisture capture film formed from this composition and adhesiveness with a board | substrate or an organic electroluminescent layer can be improved.

The polymerizable compound (C) is a compound having a polymerizable group.
A polymeric compound (C) may be used individually by 1 type, and may use 2 or more types together.
Examples of the polymerizable compound (C) include compounds having a cyclic ether group such as a compound having an epoxy group and a compound having an oxetanyl group; and a compound having a polymerizable double bond.

As a compound having an epoxy group, for example,
As monofunctional epoxy compounds, 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-methyl Phenyl glycidyl ether, p-ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl and the like;
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 ether;
Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
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 an oxetanyl group, for example,
Monofunctional oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dode). Siloxymethyl) oxetane, 3-ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane and the like;
As the polyfunctional oxetane compound, xylylene bisoxetane, 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, from the viewpoint of enhancing the crosslinking reactivity, the compound having a cyclic ether group is preferably a compound having an epoxy group, more preferably a polyfunctional epoxy compound, a polyglycidyl ether of a polyhydric alcohol, 3,4- A compound having an epoxycyclohexyl group is more preferable, and polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate 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 a (meth) acrylate compound, a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound are mentioned, for example.

  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 glycol diene, from the viewpoint of enhancing crosslinking reactivity. Methacrylate is more preferable, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferable.

  In the composition used in the present invention, the content when the polymerizable compound (C) is used is preferably 10 to 3000 parts by mass, more preferably 50 to 2000 parts by mass with respect to 100 parts by mass of the component (A). preferable. By making content of a polymeric compound (C) into the said range, the adhesiveness to the board | substrate and organic electroluminescent layer of a moisture capture film can be improved effectively.

[Radical polymerization initiator (D)]
The composition for forming a moisture capturing film used in the present invention can further contain a radical polymerization initiator (D). The composition used in the present invention contains an initiator (D), for example, an alcohol compound (iii-1-1) and a metal hydroxide formed by the hydrolysis reaction shown in the above chemical reaction formula (Iii-1-2) is efficiently fixed and easily retained in the moisture trapping film formed from the composition.

An initiator (D) may be used individually by 1 type, and may use 2 or more types together.
Examples of the initiator (D) include thermal radical polymerization initiators such as azo compounds and peroxides; thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salts. And photoradical polymerization initiators such as benzene compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, and imide sulfonate compounds.

  In the composition used in the present invention, the content when the radical polymerization initiator (D) is used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A), 2 parts by mass is more preferable. By making content of an initiator (D) into the said range, the desired radical polymerization reaction can be advanced rapidly.

[Other optional ingredients]
The composition used in the present invention can further contain other optional components. Examples of other optional components include silicone rubber, silicone oil, and diene polymer in order to relieve the stress of the formed moisture capturing film. Other examples include silane coupling agents, surfactants, pigments such as carbon black, dyes, antioxidants, stabilizers, heat transfer fillers, carbodiimide compounds, and other additives.

  Examples of the silane coupling agent include KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and also described in JP 2006-171670 A, JP 2006-184908 A, and JP 2011-007864 A. Mention may also be made of compounds. As surfactant, the compound described in Unexamined-Japanese-Patent No. 2012-226181 and Unexamined-Japanese-Patent No. 2013-23414 can be mentioned, for example.

  Examples of the diene polymer include styrene / butadiene copolymer and its hydride, styrene / isoprene copolymer and its hydride, styrene / butadiene / styrene block copolymer and its hydride, and styrene / isoprene. -Styrene block copolymers and hydrides thereof are mentioned. Also, WO 2004-055064 pamphlet, JP-A No. 04-224813, JP-A No. 09-095507, JP-A No. 2004-197107, Mention may also be made of the compounds described in Japanese Utility Model Publication No. 2007-254692.

  Examples of the carbodiimide compound include polycarbodiimide, and JP-A 05-178594, JP-A 09-124582, JP-A 10-067978, JP-A 2007-138080, International Publication No. The compounds described in the pamphlet of 2008-081230 and the pamphlet of international publication 2010-072111 can also be mentioned.

[Method for Preparing Composition for Forming Moisture Capture Film]
The composition for forming a moisture capturing film used in the present invention is a mixture of the component (A) and the component (B), and if necessary, the component (C), the component (D), and other additives at a predetermined ratio. It can be prepared by mixing.

  The composition used in the present invention can be suitably used as a moisture capturing film for producing an organic EL device in which moisture is likely to deteriorate the characteristics. For example, a moisture capturing film formed by irradiating and / or heating a coating film made of the composition can absorb moisture in the device over a long period of time. Moreover, it is also possible to re-express the moisture capturing ability of the composition by irradiating and / or heating the moisture capturing film disposed in the organic EL element.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description of Examples and the like, “part” means “part by mass” unless otherwise specified.

[ 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.).

[Synthesis of Moisture Capture Agent (A1)]
[Synthesis Example 1] Synthesis of water trapping agent (AO-1) A reactor equipped with a stirrer, a cooler, a temperature control device, and a solvent recovery device, 53.0 parts of methyl orthoformate, 2-butyl-2-ethyl −1,3-propanediol 80.0 parts, pentaerythritol 17.0 parts and 90 wt% formic acid aqueous solution 0.5 part were charged, and maintained at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. . Thereafter, the temperature was raised to 175 ° C. over 2 hours, and 46.5 parts of methanol was recovered to obtain a water capturing agent (AO-1) as a colorless, transparent, viscous polyorthoester.

When ¹ H-NMR of the moisture trapping agent (AO-1) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 0.76 to 0.96 (24H, m), δ 1.20 to 1.40 (24H, m), δ 1.10 to 1.60 (32H, m), δ 3.. 34-4.10 (24H, m), δ 5.24 (4H, s).

[Synthesis Example 2] Synthesis of water trapping agent (AO-2) A reactor equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device was added to 53.0 parts of methyl orthoformate, trimethylolpropane monoallyl ether 80. 0.0 parts, 17.0 parts of pentaerythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off the methanol produced by the alcohol exchange reaction. Then, it heated up to 175 degreeC over 2 hours, and 46.5 parts of methanol were collect | recovered, and the water | moisture-content capture agent (AO-2) was obtained as a colorless, transparent and viscous polyorthoester.

When ¹ H-NMR of the moisture trapping agent (AO-2) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 0.83 (12H, m), δ 1.24 to 1.56 (8 H, m), δ 3.20 to 4.10 (40 H, d), δ 5.10 to 5. 36 (12H, m), δ 5.88 (4H, m).

[Synthesis Example 3] Synthesis of Water Capture Agent (AO-3) In a reactor equipped with a stirrer, cooler, temperature control device and solvent recovery device, 50.0 parts of water capture agent (AO-1), t- 3.0 parts of butoxypotassium was charged and stirred at 160 ° C. for 6 hours under a nitrogen atmosphere. Thereafter, 0.6 parts of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an alkali adsorbent and treated at 120 ° C. for 1 hour. A water scavenger (AO-3) was obtained as an ortho ester.

When ¹ H-NMR of the moisture trapping agent (AO-3) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ0.87 (12H, m), δ1.40 (8H, m), δ1.55 (12H, d), δ3.20 to 4.20 (24H, d), δ3 .25 to 4.10 (32H, m), δ 4.25 to 4.45 (4H, m), δ 5.10 to 5.40 (4H, m), δ 5.80 to 6.15 (4H, m) .

[Synthesis Example 4] Synthesis of water trapping agent (AO-4) A reactor equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device, 63.0 parts of methyl orthoformate, 55.0 parts of glycerin, penta 20.0 parts of erythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. Then, it heated up to 175 degreeC over 2 hours, 57.0 parts methanol was collect | recovered, and also it concentrated on 175 degreeC and 300 Pa conditions, and removed the volatile component. A water scavenger (AO-4) was obtained as a polyorthoester having a colorless and transparent viscosity.

When ¹ H-NMR of the moisture trapping agent (AO-4) was measured, it was as follows.
¹ H-NMR (CDCl ₃ ); δ 3.20-4.20 (24H, m), δ 4.20-4.70 (4H, m), δ 5.60-6.10 (4H, m).

[Preparation of composition for forming moisture capturing film]
Moisture trapping agent (A) (component (A)), acid generator (B1) (component (B)), and polymerizable compound (C) used in the preparation of the composition for forming a moisture trapping film such as Preparation Examples ( Component (C)) is shown below.

<Ingredient (A)>
AO-1: [Synthesis Example 1]
AO-2: [Synthesis Example 2]
AO-3: [Synthesis Example 3]
AO-4: [Synthesis Example 4]
AK-1: OXT-191 (manufactured by Toagosei Co., Ltd.)

AS-1: 4-methylcyclohexanedicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
AS-2: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride
(Manufactured by Tokyo Chemical Industry Co., Ltd.)
AC-1: Calcium oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Component (B)>
B-1: CPI-210S (manufactured by Sun Apro Co., Ltd.)

(X = Special phosphorus anion)

<Ingredient (C)>
C-1: Celoxide 2021P (manufactured by Daicel Corporation; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate)

[Preparation Example 1]
Weigh out 23 parts of (AO-1) as the moisture scavenger (A), 2 parts of (B-1) as the acid generator (B1), and 75 parts of (C-1) as the polymerizable compound (C), Thorough mixing was performed using a planetary stirrer (Awatori Nertaro, Shinky). Then, defoaming was performed under vacuum to prepare a composition for forming a moisture capturing film.

[Preparation Examples 2-8 and Comparative Preparation Examples 1-2]
In Preparation Example 1, a composition for forming a moisture trapping film was prepared in the same manner as in Preparation Example 1 except that the components and the amounts shown in Table 1 were used.

[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 a light emitting layer having a thickness of 70 nm, and then baked at 60 ° C. for 10 minutes. On the 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, and 20 nm / sec was deposited thereon. A cathode was formed by laminating 100 nm of Al at a speed. In this way, an organic EL layer was formed on the glass substrate.

Next, on the organic EL layer formed on the glass substrate, the coating composition for forming the moisture capturing film was applied at a coating speed of 2 cm / sec using a bar coater “E-789” (Yoshimi Seiki Co., Ltd.) having a gap size of 100 μm. Was applied to form a coating film having a thickness of 50 μm. The film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation). The resulting coating film was exposed using a PLA-501F exposure machine (extra-high pressure mercury lamp, manufactured by Canon Inc.) so that the integrated dose was 30000 J / m ^2, and then in a clean oven Was heated at 80 ° C. for 1 hour to form a moisture capturing film as a cured product on the organic EL layer on the glass substrate.

Next, a composition having the same composition as the moisture trapping film-forming composition obtained in Comparative Preparation Example 1 was applied to the peripheral edge of the film-formed glass substrate using a dispenser. A film was 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 (strength at 365 nm is 100 mW). After irradiating with ultraviolet light for 30 seconds, the coating film was cured by heating at 80 ° C. for 30 minutes to form a sealing material.
The organic EL element was manufactured as described above.

[Evaluation]
The following evaluation was performed about the said composition for moisture capture film formation, hardened | cured material, and an organic EL element.

<Adhesiveness>
Two pieces of glass obtained by cutting a glass substrate having a thickness of 0.7 mm into 25 mm × 75 mm were prepared. A coating film having a film thickness of 100 μm was formed by applying the moisture trapping film-forming composition to the center of one glass piece, and the two glass pieces were crossed in a cross shape and adhered through the coating film. . Using a PLA-501F exposure machine (extra-high pressure mercury lamp, manufactured by Canon Inc.), the exposure is performed so that the integrated dose becomes 30000 J / m ^2, and then heated at 80 ° C. for 1 hour in a clean oven. By this, the said coating film was hardened. The glass substrate was peeled up and down under the condition of a peeling speed of 150 mm / min, and the maximum load was divided by the application area of the composition measured in advance to obtain an adhesive force (unit: MPa).

<Visible light transmittance>
A glass substrate having a thickness of 0.7 mm was cut into 25 mm × 75 mm, and the composition for forming a moisture capturing film was applied at a film thickness of 100 μm. Using a PLA-501F exposure machine (extra-high pressure mercury lamp, manufactured by Canon Inc.), the exposure is performed so that the integrated dose becomes 30000 J / m ^2, and then heated at 80 ° C. for 1 hour in a clean oven. This was cured to form a moisture capturing film on the glass substrate. This was measured with a UV-VIS measuring apparatus (JASCO V650), with the glass substrate as a reference, and the visible light transmittance (400 to 800 nm) before and after the moisture resistance test (85 ° C., 85 RH%, 200 hours) was measured.

<Moisture resistance test>
The ratio (%) of the dark spot generated when the organic EL element obtained above was energized for 500 hours under the conditions of 85 ° C. and 85 RH% to the surface area of the upper surface of the organic EL layer was measured. When this ratio was 5% or less, it was judged that the moisture resistance was good, that is, the occurrence of dark spots was suppressed.

DESCRIPTION OF SYMBOLS 10 Substrate 20,201 Sealing material 30 Sealing member 40 Organic EL layer 50, 501, 510 Moisture trapping film 502, 503 Support material 100, 101, 200, 300, 400 Organic EL element

Claims (7)

A substrate,
An organic EL layer formed on the substrate;
An organic EL element having a sealing member,
In the sealed space of the organic EL element,
(A) a compound having a hydrolyzable structure;
(B) An organic EL device having a moisture trapping film formed using a composition for forming a moisture trapping film containing at least one compound selected from an acid generator and a base generator. The compound (A) is at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), a carboxylic acid anhydride (A2) and at least one selected from the group consisting of at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) Yes,
The organic EL device according to claim 1, wherein the compound (B) is an acid generator.
[In formula (A1-1), R ^{1 to} R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group or a carbon number. 1 to 18 organic groups, and two or more groups selected from R ³ , R ⁴ and R ⁷ are bonded to each other to form a cyclic structure together with the carbon atoms to which they are directly bonded. N is 0 or an integer of 1 to 18, and * represents a bonding position; in formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each ⁸ is independently an organic group having 3 to 10 carbon atoms. ]
[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, 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 is 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 number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca A pto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30. ] The compound (A) is at least one compound (A3) selected from the carboxylic acid anhydride (A2), the compound represented by the formula (A3-1), and the compound represented by the formula (A3-2). At least one selected from the group consisting of:
The organic EL device according to claim 1, wherein the compound (B) is a base generator.
[In the formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom or a zirconium atom; R ¹ represents a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, 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 is 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 number 6-14, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, or merca A pto 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 moisture capturing film forming composition is
(C) The organic EL device according to any one of claims 1 to 3, further comprising a polymerizable compound.   The organic EL element according to claim 1, wherein the organic EL layer has a structure in which an organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other.   The organic EL element according to claim 1, wherein the moisture capturing film is disposed so as to be separated from the sealing member. (A) a compound having a hydrolyzable structure;
(B) a moisture trapping film formed using a moisture trapping film-forming composition containing at least one compound selected from an acid generator and a base generator;
A moisture capturing film disposed in a sealing space of an organic EL element having a substrate, an organic EL layer formed on the substrate, and a sealing member.