KR20150057957A - Organic electroluminescene device and water trap film - Google Patents

Abstract

Provided is an organic EL device capable of excluding moisture influence to an organic EL layer for the better efficiency. [Solutions] The organic EL device of the present invention includes a substrate, an organic EL layer formed on the substrate, and an encapsulation member, and includes a moisture trap film, in the space of encapsulation member of the organic EL device, which is formed by using a composition for forming a moisture trap film having (A) a compound having a structure which can hydrolyze, and (B) at least one compound selected from an acid generator and a base generator.

Description

ORGANIC ELECTROLUMINESCENT DEVICE AND WATER TRAP FILM BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to an organic EL device and a moisture trapping film.

In recent years, organic electroluminescence (EL) devices are one of the electronic devices that are being actively developed. The organic EL device is a simple device having a laminate structure (organic EL layer) composed of a positive electrode / organic light emitting layer / negative electrode as a basic structure and is a light emitting device capable of obtaining bright light emission. However, the problem that the organic light emitting layer is susceptible to moisture I have.

That is, the organic EL element is concerned with the formation of a so-called dark spot due to the influences of moisture penetrated into the element along with the prolongation of the driving period, and there is a concern that the luminescence characteristics such as luminance and luminous efficiency are gradually lowered I have.

Thus, in the organic EL element, a sealing structure for blocking the organic light-emitting layer from the atmosphere becomes indispensable, and a sealing member made of metal or glass and a substrate on which the organic EL layer is formed are bonded to each other using a suitable sealing material, A technique of sealing an organic EL layer in a sealing space formed between the sealing member and the sealing member has been examined.

Further, in the organic EL device, a technique using a desiccant has been studied to more effectively eliminate the influence of moisture. For example, a technique of keeping a low humidity environment by disposing a desiccant such as particles of phosphorous pentoxide at a position spaced apart from the positive electrode and the negative electrode in the sealing space in which the organic light emitting layer is sealed is known, (See, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 03-261091

In the organic EL device, it is required to use the device in an airtight state in which moisture in the device is removed and moisture is prevented from intruding from the outside. However, in the prior art in which the desensitizing agent is disposed so as to be separated from the anode and the cathode that sandwich the organic light-emitting layer in the sealing space by using a phosphorus pentoxide particle or the like known as a drying agent in the drying space, It was difficult to fully exclude.

Thus, in the organic EL element, a moisture trapping technique capable of efficiently removing moisture in the sealed space in which the organic EL layer is sealed, and a water trapping technique capable of efficiently removing the influence of moisture on the organic EL layer An EL element is required.

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 device and a moisture trapping film which can efficiently eliminate the influence of moisture on the organic EL layer.

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

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

[1] An organic EL device having a substrate, an organic EL layer formed on the substrate, and a sealing member, wherein a compound having a structure capable of hydrolyzing (A) and (B) ) An organic EL device having a water-trapping film formed by using a composition for forming a moisture-trapping film containing at least one compound selected from an acid generator and a base generator.

[2] The positive resist composition according to the above item [1], wherein 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) ), At least one compound selected from the group consisting of a compound represented by the formula (A3-1) and a compound represented by the formula (A3-2), and the compound (B) is at least one compound selected from the group consisting of , The organic EL device of [1] above, which is an acid generator:

Wherein R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or a group having 1 to 18 carbon atoms And 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 atoms to which they are bonded directly, and n is 0 or An integer of 1 to 18, and * represents a bonding position; In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each R ⁸ is independently an organic group having 3 to 10 carbon atoms;

[In the formulas (A3-1) and (A3-2), X is a silicon atom, a titanium atom or a zirconium atom; R ¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group and an isocyanate group, An alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group; R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxyl group, a glycidoxy group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, or a mercapto group; p is an integer from 0 to 6; r is an integer of 0 to 2, and s is an integer of 1 to 30;

[3] The resin composition according to any one of [1] to [3], wherein the compound (A) is at least one compound (A3) selected from a carbonic acid anhydride (A2), a compound represented by the formula (A3-1) , And the compound (B) is a base generator. The organic EL device according to the above [1], wherein the compound (B) is a base generator.

[4] The organic EL device according to any one of [1] to [3], wherein the moisture trapping film forming composition further comprises (C) a polymerizable compound.

[5] The organic EL device 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.

[6] The organic EL device according to any one of [1] to [5], wherein the moisture trapping film is disposed so as to be spaced apart from the sealing member.

[7] A water-trapping film-forming composition formed by using a water-trapping film-forming composition containing (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 an encapsulation space of an organic EL element having a substrate, an organic EL layer formed on the substrate, and a sealing member.

According to the present invention, it is possible to provide an organic EL element capable of effectively eliminating the influence of moisture on the organic EL layer and a moisture trapping film capable of effectively eliminating the influence of moisture on the organic EL layer. Therefore, according to the present invention, it is possible to provide an organic EL element such as an organic EL light or an organic EL display element which can suppress the occurrence of a dark spot even when driven for a long time. Therefore, the organic EL device of the present invention can be suitably used for a TV or a portable information device requiring high reliability.

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

(Mode for carrying out the invention)

The organic EL device and the moisture trapping film of the present invention will be described.

[abandonment EL  device]

An organic EL device of the present invention is an organic EL device having a substrate, an organic EL layer formed on the substrate, and a sealing member used for sealing the organic EL layer, wherein in the sealing space of the organic EL device, And a water-trapping film formed using a composition for forming a water-trapping film.

<Board>

As the substrate (substrate for element) of the organic EL element, a substrate having excellent visible light transmittance and low oxygen permeability and moisture permeability is used, and examples thereof include a glass substrate and a transparent resin substrate. As the constituent material of the substrate, for example, glass such as alkali-free glass; Polyolefins such as polyethylene, polypropylene, alicyclic polyolefins, polystyrene, triacetylcellulose, polyimides, fluorinated polyimides, polyamides, polyamides, polyamides, , Polyamideimide, polyetherimide, polyarylate, polyether sulfone, polysulfone, polyether ether ketone, polycarbonate, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, polyvinyl chloride, polyvinylidene chloride, poly Urethane, and (meth) acryloyl compounds. The substrate is not limited to the above example.

<abandonment EL layer>

The organic EL layer of the organic EL element 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, specifically, a structure in which an anode and a cathode (A laminated structure composed of an anode / an organic light emitting layer / a cathode) sandwiched between the anode and the cathode as a basic structure and can take various structures as described later.

The organic luminescent layer contains a luminescent material which is an organic material, that is, an organic luminescent material. The organic light emitting material contained in the organic light emitting layer may be a low molecular weight organic light emitting material or a high molecular weight organic light emitting material. For example, a base matrix such as Alq ₃ (tris (8-quinolinolate) aluminum), BeBq ₃ (bis (10-hydroxybenzo [h] quinolinate) beryllium) Or a material doped with orcumarin can be used. When the coating method of the organic luminescent material by the ink jet method is used, it is preferable that the polymer organic luminescent material is suitable for the method. Examples of the polymer organic light emitting material include polyphenylene vinylene and derivatives thereof, polyacetylene and derivatives thereof, polyphenylene and derivatives thereof, poly para phenylene ethylene ) And derivatives thereof, poly 3-hexyl thiophene (P3HT) and derivatives thereof, polyfluorene (PF) and derivatives thereof, and the like.

The anode and the cathode of the organic EL layer are each made of a conductive material.

As the material of the anode of the organic EL layer, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), tin oxide and the like are selected.

Further, 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 a hole injection layer and an intermediate layer are disposed between the anode and the organic light emitting layer, a hole injection layer is disposed on the anode, an intermediate layer is disposed on the hole injection layer, and an organic light emitting layer is disposed on the intermediate layer. Further, the hole injection layer and the intermediate layer may be omitted as long as the hole can be efficiently transported from the anode to the organic emission layer.

As the material of the cathode of the organic EL layer, for example, ITO, IZO and tin oxide can be selected. It is also possible to select, for example, barium (Ba), barium oxide (BaO), aluminum (Al), an alloy containing Al, and the like.

In the organic EL layer, an electron injection layer made of, for example, barium (Ba) or lithium fluoride (LiF) may be disposed between the cathode and the organic emission layer.

&Lt; Sealing member &

As the sealing member, a member having a low oxygen permeability and a low water permeability is used, and for example, a member made of glass, resin or the like can be mentioned. As the constituent material of the sealing member, a resin such as polyethylene terephthalate, polyethylene naphthalate and polyimide may be used as the substrate, and the resin exemplified in the column of <substrate> may be mentioned. The sealing member may be 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, a substrate formed of a material obtained by kneading an inorganic material and a resin, It is also possible to use a substrate on which an inorganic material is deposited or applied.

The sealing member is fixed to the substrate by, for example, a sealing member. As the sealing material of the organic EL element, an adhesive resin material is used, and a thermosetting or photo-curable 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 a silicone resin, an acrylic resin, an epoxy resin, a polyimide, and a urethane resin.

The state of fixing the substrate and the sealing member using the sealing material is not particularly limited. For example, the sealing member may be fixed to the substrate by forming a sealing material on the peripheral portion of the organic EL layer in the substrate. In this case, the organic EL element has a hollow structure. Further, the inter-electrode space (hollow structure) in the organic EL device may be further filled with a sealing material.

For example, an organic EL layer formed on a substrate is accommodated in an encapsulation space formed by the structure, by a structure having a substrate, a sealing material, and a sealing member fixed to the substrate by a sealing material, It is possible to prevent contact with the outside air.

<Moisture-trapping film>

The moisture trapping film of the present invention is formed from a composition for forming a moisture trapping film which will be described later. The moisture trapping film efficiently removes moisture in the organic EL device and can efficiently remove the influence of moisture on the organic luminescent layer. The water-trapping film is difficult to generate highly volatile decomposition products such as low-molecular alcohol even in the state of capturing moisture. When used in an organic EL device, the moisture- The occurrence of spots can be suppressed.

The location of the moisture-trapping film in the sealing space of the organic EL device is not particularly limited. The moisture trapping film may be disposed on the organic EL layer in such a manner as to be in surface contact with the organic EL layer (for example, to cover the surface of the organic EL layer on the sealing member side) and to be spaced apart from the sealing member Good; Or may be formed so as to be in surface contact with the side surface of the sealing material (for example, so as to cover the surface on the side of the sealing space of the sealing material).

The moisture trapping film may be supported or sandwiched by a supporting member.

As the supporting member for supporting the water-trapping film and the pair of supporting members for holding the water-permeable film, a transparent resin substrate or the like can be used. As the constituent material of the support material, for example, transparent resins such as polyethylene terephthalate, polyethylene naphthalate, polyimide and triacetylene cellulose can be mentioned. In addition, the resin exemplified in the column of <substrate> can be mentioned.

The moisture trapping film and the moisture trapping film supported or sandwiched by the support material can be disposed in other sealing spaces on the organic EL layer using, for example, a known pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include a material which can be adhered to other adherend with extremely low pressure such as pressure by a finger without requiring the help of heat or solvent. For example, as the pressure-sensitive adhesive, materials such as rubber, acrylic, and silicone can be used.

Further, in the case where the moisture trapping film and the moisture trapping film supported or sandwiched by the support material are fixed more strongly on the organic EL layer, a curable pressure sensitive adhesive may be used as the pressure sensitive adhesive. Examples of the preferable curing type pressure-sensitive adhesive include urethane pressure-sensitive adhesives, epoxy pressure-sensitive adhesives, water-based polymer-isocyanate pressure-sensitive adhesives, and thermosetting acrylic pressure-sensitive adhesives.

In addition, the composition for forming a water-trapping film is excellent in adhesiveness, and therefore, in the case of forming a water-entrapping film by applying the composition for forming a water-trapping film on the organic EL layer, an adhesive may not be used.

In the moisture trapping film supported or sandwiched by the water trapping film or the supporting member, the moisture trapping film or the supporting member may be disposed in direct surface contact with the organic EL layer or may be disposed on the organic EL layer via the pressure sensitive adhesive . For example, in the case of a water-trapping film sandwiched by a pair of supporting members, one of the supporting members may have a direct surface contact with the organic EL layer, and one of the supporting members may be bonded to the organic EL layer Or may be arranged on the surface.

It is possible to suppress the peeling of the moisture trapping film from the organic EL layer or the like by disposing the moisture trapping film supported or sandwiched by the moisture trapping film or the support material on the organic EL layer or the like using a pressure sensitive adhesive to improve the reliability of the moisture trapping film Can be improved.

The organic EL device of the present invention having the above structure can remove water in the sealed space in which the organic EL layer is accommodated by having the moisture trapping film of the present invention. Further, the moisture-trapping film of the present invention can absorb moisture for a long period of time, and can suppress deterioration of the organic EL element due to moisture. That is, the moisture-trapping film of the present invention can efficiently remove the influence of moisture on the organic light-emitting layer of the organic EL device. Therefore, the organic EL element can constitute, for example, an organic EL lighting apparatus or an organic EL display element having high reliability.

As a method of forming the moisture trapping film, for example, a step 1 in which a coating film is formed on an organic EL layer formed on a substrate by using a composition for forming a water trapping film which will be described later, the coating film is irradiated with radiation, , Or a step 2 in which irradiation with radiation and heating are carried out.

Further, an organic EL device may be formed using a moisture-capturing film formed in advance. In the case of forming the moisture-trapping film supported by the support material, for example, a step 1 'of forming a coating film using a composition for forming a water-trapping film on a support material, the coating film is irradiated with radiation, , Or a step 2 'in which irradiation with radiation and heating are carried out. In the case of forming the moisture trapping film sandwiched by the pair of supporting members, for example, after the step 1 ', the other supporting member is bonded onto the coating film before the step 2'. The water-trapping film thus obtained is placed on the organic EL layer, for example, using a pressure-sensitive adhesive as necessary.

The composition for moisture trapping film formation can be applied on the organic EL layer to be coated or on the support material by, for example, a spin coater, a roll coater, a spray coater, a bar coater, a dispenser and an ink jet apparatus.

As the radiation in Processes 2 and 2 ', the hydrolysis reaction described below can be carried out in the above-mentioned composition, and there is no particular limitation so long as the coating film can be cured. However, visible rays, ultraviolet rays, And a charged particle beam, and ultraviolet rays are preferable. In the case of performing the heating in the processes 2 and 2 ', the heating temperature is preferably 30 to 200 캜, more preferably 50 to 150 캜; The heating time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours.

The composition may be irradiated with radiation in the processes 2 and 2 'by known methods and conditions. For example, a high-pressure mercury lamp is used to irradiate the composition with ultraviolet rays (e.g., 500 to 15000 mJ / .

The film thickness of the water-trapping film is not particularly limited, but is, for example, 1 to 500 m, preferably 5 to 200 m, more preferably 5 to 100 m. The film thickness of the film can be measured, for example, by Depth Gage 547-251 (manufactured by Mitsutoyo Co., Ltd.).

The moisture-trapping film has excellent visible light transmittance even under a humid environment. Therefore, even if the organic EL device is disposed in the sealed space of the organic EL device, there is no fear of hindering the emission characteristics of the organic EL device.

Since the water-trapping film of the present invention is formed of a composition for forming a water-trapping film which will be described later, by disposing the moisture-trapping film in the sealing space of the organic EL device, the removal of moisture in the sealing space, It can be done well.

"abandonment EL  Element Concrete example "

Several examples of embodiments of the organic EL device of the present invention will be described with reference to the drawings.

1 has a substrate 10, a sealing material 20 and a sealing member 30 fixed to the substrate 10 by a sealing material 20, and the substrate 10 An organic EL layer 40 formed on the substrate 10 and a moisture trapping film 50 formed on the organic EL layer 40 are formed in the sealing space formed by the seal member 20, And a gap between the moisture trapping film 50 and the sealing member 30 is formed in the sealing space. That is, the organic EL element 100 is brought into surface contact with the organic EL layer 40 (so as to cover the surface of the organic EL layer 40 on the side of the sealing member 30) And a moisture trapping film 50 disposed on the organic EL layer 40 so as to be spaced apart from the organic EL layer 40.

It is also possible to fill the above-mentioned gap in the sealing space with a sealing material so as not to form a gap in the sealing space. The organic EL device 200 shown in Fig. 2 is a device in which the sealing material 201 corresponding to the sealing material 20 of the organic EL element 100 shown in Fig. 1 is sandwiched between the substrate 10 and the sealing member 30 As shown in FIG. The sealing material 201 fixes the substrate 10 and the sealing member 30 and closes the sealing space formed between the substrate 10 and the sealing member 30 without any gap. With this structure, the sealing material 201 can protect the organic EL layer 40 and the moisture trapping film 50 formed on the substrate 10. As a result, the reliability performance of the organic EL element 200 can be improved.

The moisture trapping film 50 is formed directly in contact with the organic EL layer 40 in the organic EL devices 100 and 200 shown in Figs. 1 and 2. However, the present invention is not limited to such a structure, Or may be formed through a pressure-sensitive adhesive. In addition, for example, it is also possible to support or hold the moisture trapping film with a suitable support material, and arrange the moisture trapping film together with the support material on the organic EL layer. Figs. 3 and 4 are the organic EL elements 300 and 400 in Figs. 1 and 2, respectively, in which the arrangement of the moisture trapping film is changed to this form.

In the organic EL elements 300 and 400 shown in Figs. 3 and 4, the moisture trapping film 501 sandwiched by the pair of supporting members 502 and 503 is sandwiched between the organic EL layer 40 As shown in Fig. That is, the supporting material 503 and the organic EL layer 40 are bonded together by an adhesive. In the organic EL elements 300 and 400 shown in Figs. 3 and 4, in the sealing space between the organic EL layer 40 and the sealing member 30, the organic EL layer 40 The water trapping film 501 sandwiched between the pair of supporting members 502 and 503 is disposed so as to be in surface contact with the sealing member 30 and to be separated from the sealing member 30. [

4, the sealing material 201 corresponding to the sealing material 20 of the organic EL element 300 shown in Fig. 3 is bonded to the substrate 10 and the sealing member 30, As shown in Fig. The sealing material 201 fixes the substrate 10 and the sealing member 30 and closes the sealing space formed between the substrate 10 and the sealing member 30 without any gap.

5 has a substrate 10, a sealing material 20, and a sealing member 30 fixed to the substrate 10 by a sealing material 20, and the substrate 10 An organic EL layer 40 formed on the substrate 10 and a moisture trapping film 40 formed so as to be in surface contact with the side surface of the sealing material 20 are formed in the sealing space formed by the seal member 20, (510). Here, the sealing material 20 is formed on the periphery of the organic EL layer 40 in the substrate 10.

[Composition for forming moisture trapping film]

The water-trapping film-forming composition 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. Further, it is preferable that the composition further contains a polymerizable compound (C).

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

[moisture Capture agent  (A)]

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

<moisture Capture agent  (A1) &gt;

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

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

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

Examples of the organic group having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, Straight or branched chain alkyl group having 1 to 18 carbon atoms, preferably alkyl group having 1 to 6 carbon atoms, such as hexyl, decyl, dodecyl and octadecyl; Cycloalkyl groups having 3 to 12 carbon atoms such as cyclohexyl and methylcyclohexyl; Cycloalkyl substituted alkyl groups having 4 to 18 carbon atoms such as cyclohexylmethyl and cyclohexylethyl; A phenyl group; Aralkyl groups having 7 to 18 carbon atoms such as phenyl-substituted alkyl groups (e.g., benzyl group, phenethyl group); A group in which a part of these groups is substituted with an oxygen atom (hereinafter also referred to as &quot; oxygen atom substituent &quot;); Vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, glycidyl group; A carboxyl group, and may be a group represented by the following formulas g1 to g7;

Examples of the "organic group having 3 to 10 carbon atoms" include at least one kind of group selected from "vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group and glycidyl group" Having 3 to 10 carbon atoms, and groups represented by the following formulas g1 to g7 may 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 the formula (A1-1), the sum of the carbon numbers of the groups represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ (when n is 0, the number of carbon atoms of R ² to R ⁵ Is preferably from 0 to 18, more preferably from 0 to 12, from the viewpoints of the absorption ability and the solubility.

Two or more groups selected from R ³ , R ⁴ and R ⁷ (in the case of n = 0, R ³ and R ⁴ ) are bonded to each other to form a cyclic structure with the carbon atoms to which they are bonded directly There may be. Examples of the cyclic structure include a cyclohexane ring and a cyclopentane ring.

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

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

Formula (A1-1) of, R ⁶ ~R ⁷ are, each independently represent a hydrogen atom, a hydroxyl group, the above-mentioned alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a cycloalkyl group-substituted alkyl group having a carbon number of 4-18 carbon atoms, 3 to 12 , A phenyl group, an aralkyl group having 7 to 18 carbon atoms, an oxygen atom substituent, a vinyl group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, glycidyl group, carboxyl group, Is preferably a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by any of the above formulas g1 to g2.

R ¹ to R ⁷ are preferably the above-mentioned atom or group from the viewpoints of the absorption ability as a water trapping agent and the compatibility with other components (compatibility).

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

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

&Quot; Compound having a structural moiety represented by formula (A1-1) &quot;

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

Wherein A is a structural moiety represented by formula (A1-1); Y is a residue other than a hydroxyl group of m (2? M? P) from a hydroxyl group-containing compound (a3), which has p (p? 2) hydroxyl groups in one molecule; m is an integer of 2 to p.

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

The orthoester (a1)

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

In formula (a1), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; And each Ra is independently an organic group having 1 to 18 carbon atoms. The organic group is preferably the straight chain or branched chain alkyl group having 1 to 18 carbon atoms, the cycloalkyl group having 3 to 12 carbon atoms, or the cycloalkyl substituted alkyl group having 4 to 18 carbon atoms, and the straight or branched chain More preferably an alkyl group having 1 to 6 carbon atoms.

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

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

The polyhydric alcohol (a2)

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

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

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

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

Examples of the? -glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dihydroxycyclohexane, pinacol, hydrolyzate of long chain alkyl monoepoxide; Fatty acid monoglycerides (? Form) such as glycerin monoacetate (? Form) and glycerin monostearate (? Form); 3-ethoxypropane-1,2-diol, and 3-phenoxypropane-1,2-diol. Of these, ethylene glycol, 1,2-propylene glycol and 1,2-hexanediol are preferred.

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

Examples of the compound wherein n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 1,3-pentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, (Hydroxymethyl) -2-ethylpropane-1,3-diol, glycerin, 2-phenoxypropane-1, 1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylol propionic acid, dimethylolbutanoic acid, 2-ethyl- Octanediol, 1,3-dihydroxycyclohexane; Glycerin monoacetate (? -Form), glycerin monostearate (? -Form), and other fatty acid monoglycerides (? -Form). Among these, preferred are neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, Propylene diol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, ) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol and glycerin.

The hydroxyl group-containing compound ( a3 )

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

When the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, the hydroxyl group-containing compound (a3) may be introduced from the polyhydric alcohol (a2) You can also choose to use it. In this case, as the compound selected as the hydroxyl group-containing compound (a3), a compound other than the compound selected as the polyhydric alcohol (a2) is preferably selected.

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

Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5- Methyl-1,5-pentanediol, 1,4-dimethylol cyclohexane, tricyclodecanedimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate Bisphenol A, bisphenol F, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3 Tetraoxaspiro [5,5] undecane, diethylene glycol, triethylene glycol, polyethylene glycol higher than tetra, Propylene glycol, dipropylene glycol, tripropylene glycol, tetraester or higher polypropylene glycol, ethylene oxide and propylene oxide copolymerized with a hydroxyl group at both ends There may be mentioned straight-chain polyester, polycarbonate, a carboxylic acid addition product of a diol, a diepoxide having a hydroxyl group at both terminals such as a copolymer, a polycaprolactone diol.

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

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

Reaction rate

(A1), the polyhydric alcohol (a2) and the hydroxyl group-containing compound (a3) are reacted with each other to produce the water capturing agent (A1) (a3) is not particularly limited.

For example, the amount of the orthoester (a1) is in the range of 0.01 to 10 mol, preferably 0.05 to 5 mol, more preferably 0.1 to 2 mol, relative to 1 molar equivalent of the hydroxyl group in the hydroxyl group-containing compound (a3) And the amount of the polyhydric alcohol (a2) is in the range of 0.01 to 10 moles, preferably 0.05 to 5 moles, and more preferably 0.1 to 2 moles, from the viewpoint of ease of molecular weight control and the like It is suitable. When the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2), the compound selected as the hydroxyl group-containing compound (a3) other than the compound selected as the polyhydric alcohol (a2) is selected.

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

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

A compound having a structural moiety represented by the formula (A1-1) Concrete example

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

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

In the formula (A1-ii), Y ² is a divalent residue excluding two hydroxyl groups from a compound having two hydroxyl groups in one molecule. R ¹ to R ⁷ and n are the same as R ¹ to R ⁷ and n in formula (A1-1). The above compound can be synthesized by using, for example, an orthoester 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 the formulas (A1-ⅲ), Y ³ is a residue tetravalent except that four hydroxyl groups from a compound having four hydroxyl groups in a molecule. R ¹ to R ⁷ and n are the same as R ¹ to R ⁷ and n in formula (A1-1). The compound can be synthesized by using, for example, an orthoester of the formula (a1), a polyhydric alcohol of the formula (a2-1) and a compound having four hydroxyl groups in one molecule as raw materials.

The compound represented by the formula (A1-2) Concrete example

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

<moisture Capture agent  (A2)>

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

" Monocarbonic  anhydride"

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

The anhydrides of the monocarbonic acid may be used singly or in combination of two or more.

" Dicarboxylic acid  anhydride"

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

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

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

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

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

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

The dicarboxylic anhydrides may be used singly or in combination of two or more.

" Tetracarboxylic acid 2 anhydride "

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

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

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

Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, Cyclobutane tetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane tetracarbon Acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5, 6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan- 1,3 -dione, 1,3,3a, 4,5,9b- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [l, 2-c] 5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] , 3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ Dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -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, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene- , Bicyclo [2,2,2] - Sat-7-ene can be cited a compound represented by the respective 2,3,5,6-tetracarboxylic acid dianhydride, formula (T-1) and formula (T-2).

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

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

The tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

<moisture Capture agent  (A3) &gt;

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

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

In the formulas (A3-1) and (A3-2), R ¹ represents a "(meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl 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.

In the formulas (A3-1) and (A3-2), R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, A (meth) acryloyloxy group, a glycidoxy group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, or a mercapto group.

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

When there are plural 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.

Examples of the organic group represented by R ¹ in the formulas (A3-1) and (A3-2) include groups represented by the following formulas. 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 in R ¹ in the formulas (A3-1) and (A3-2) may be either linear or branched, and examples thereof include methyl, ethyl, n-propyl, isopropyl, Isobutyl, t-butyl, pentyl and hexyl; The cycloalkyl group includes, for example, cyclohexyl.

The alkyl group in R ² in formulas (A3-1) and (A3-2) may be either linear or branched. The number of carbon atoms of the alkyl group is 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Specifically, in addition to the alkyl group exemplified for R ¹ , an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, - tridecyl group, n-tetradecyl group, and n-hexadecyl group. Examples of the cycloalkyl group for R ² in the formulas (A3-1) and (A3-2) include a cycloheptyl group and a cyclooctyl group.

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

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

As R ^{2 in the} formulas (A3-1) and (A3-2), an alkyl group and a halogen-substituted alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth) acryloyloxy group or a glycidoxy group are preferable. When a plurality of R &lt; ² &gt; exist in the same molecule, they may be the same or different.

Specific examples of the compound (A3) include a silane compound in which X is a silicon atom.

In the compound (A3-1)

Examples of the silane compound wherein r is 0 or s is 1 include alkoxysilane compounds having two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane; An alkoxysilane compound having two aromatic hydrocarbon groups having 6 to 14 carbon atoms such as diphenyldimethoxysilane; Methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane (Meth) acryloyloxy group such as 3-acryloyloxypropylethyldimethoxysilane and 3-acryloyloxypropylmethyldiethoxysilane, and an alkoxysilane compound having an alkyl group having 1 to 20 carbon atoms; 3-methacryloyloxypropylphenyldimethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldimethoxysilane, An alkoxysilane compound having a (meth) acryloyloxy group and an aromatic hydrocarbon group having 6 to 14 carbon atoms; Alkoxysilane compounds having two (meth) acryloyloxy groups such as 3,3'-dimethacryloyloxypropyldimethoxysilane and 3,3'-diacryloyloxypropyldimethoxysilane; Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysilane, and the like, An alkoxysilane compound having an alkyl group of 1 to 20; 3-glycidoxypropyldimethoxysilane, 3-glycidoxypropyldiethoxysilane, etc., and an alkoxysilane compound having an aromatic hydrocarbon group having 6 to 14 carbon atoms.

Examples of the silane compound in which r is 1 or s is 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyl Alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as triethoxysilane, ethyltriisiso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane and decyltrimethoxysilane; An alkoxysilane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane; An alkoxysilane compound having one aromatic hydrocarbon group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane; Methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane Acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltripropoxysilane. These alkoxysilane compounds may be used alone or in combination of two or more.

Examples of the silane compound wherein r is 2 or s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetrabutoxysilane, tetraphenoxy Silane, and tetrabenzyloxysilane.

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

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

The compound (A3-1) further includes a compound represented by the formula (A3-v).

As the compound (A3-2)

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

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

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

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

Examples of commercially available products of the compound (A3) include OXT-191 (manufactured by Toagosei Co., Ltd.) and X-22-3000T (manufactured by Shin-Etsu Chemical Co., Ltd.).

&Lt; Explanation of action and effect &

The function and effect of the composition for forming a water-trapping film used in the present invention will be described below.

When the composition for forming a water-trapping film used in the present invention undergoes heating and / or light irradiation, an acid or base is formed from the acid / base generating agent (B). The acid or base promotes the hydrolysis reaction of the water capturing agent (A) based on the water present in the system (system) in which the composition is used, so that water present in the system can be consumed with high efficiency . In this specification, &quot; capture of moisture &quot; is used in this meaning. The hydrolysis product of the moisture trapping agent (A) is less likely to deteriorate the performance of the organic EL device as described later.

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

Generally, the decomposition products are dispersed in the organic EL device by, for example, volatilization, and reach the organic EL layer which becomes the light emitting layer of the organic EL device to be contaminated to generate a dark spot. Which may deteriorate performance. However, in the present invention, since the hydrolysis product produced from the water entrapping agent (A) has an appropriate molecular weight, volatilization or the like is suppressed and can remain in the moisture trapping film. The larger the molecular size of the hydrolysis product is, the more likely it is to remain in the moisture trapping film, and therefore, the water trapping agent (A) is preferably a compound having a relatively large molecular weight.

The water capturing agent (A) used in the present invention is difficult to generate highly volatile hydrolyzed products such as low molecular alcohols and the like even in the state of capturing moisture, and for example, a dark spot is generated by adherence of the hydrolysis product Generation of dark spots due to the attachment of the decomposition products to the organic EL layer can be suppressed even when the organic EL device is used in an organic EL device which is easy to produce.

Examples of the hydrolysis reaction of the water entrapping agent (A) are shown below.

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

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

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

[Compound (B)]

The composition for forming a water-trapping 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 in the present invention contains the acid generator (B1), at least one member selected from the water entraining agents (A1) to (A3) is used as the water entrapping agent (A). When the composition used in the present invention contains the base generator (B2), at least one species selected from the water entrapping agents (A2) to (A3) is used as the water entrapping agent (A).

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

The radiation-sensitive acid generators and the radiation-sensitive base generators 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 serves as a catalyst for hydrolysis reaction of, for example, the aforementioned water capturing agent (A). The released basic active substance functions as a catalyst for hydrolysis reaction of, for example, the water trapping agents (A2) and (A3) described above.

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

In the composition used in the present invention, the content of the component (B) in the case of the acid generator (B1) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the component (A) 0.5 to 10 parts by mass. When the content of the component (B) is within the above range, for example, a composition having excellent radiation sensitivity can be obtained.

In the composition used in the present invention, the content of the component (B) when it is the base generator (B2) is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the component (A) 1 to 10 parts by mass. When the content of the component (B) is 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, an anion curing catalyst such as an optical or thermal cationic curing catalyst such as an iodonium salt, a sulfonium salt or a phosphonium salt, an imidazole or an acid anhydride can be used. Of these, a cationic curing catalyst is preferred, and a light cationic curing catalyst is more preferred. This is because the curing rate is high and the polymerization reaction is not initiated unless light is applied, and therefore the storage stability is good.

Specific examples of the cationic curing catalyst include cations such as iodonium, sulfonium, and phosphonium substituted with an alkyl group or an aryl group, and cations such as SbF ₆ -, BF ₄ -, B (C ₆ F ₅ ) ₄ -, PF ₆ -, P (Rf) _n F _(6-n) - (Rf is a perfluoroalkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 3), CnF _{2n + 1} SO ₃ - (SO ₂ CF ₃ ) ₂ -, C (SO ₂ CF ₃ ) ₃ -, and the like. Specific examples thereof include CPI-100P, CPI101A, CPI-200K, CPI-210S and the like (manufactured by San Ainpro), San-Aid SI-150L, Sanade SI-110L, Sanade SI- CI series such as ADI SI-80L and SANEID SI-100L (manufactured by SANSHIN KAGAKU KOGYO CO., LTD.), PI-2074 manufactured by Rhodia and CI2920 manufactured by Nippon Soda Co., Ltd., OPTOMER SP- (OPTON) CP series such as CP-series, CP-series and CP-66, WPAG series and WPI series manufactured by Wako Junyaku.

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

As the acid generator (B1), there can be mentioned, for example, Japanese Patent Laid-Open Nos. 2006-096742, 2006-282633, 2010-241733, 2012-153642, 2012-201611, JP-A-2013-100237, JP-A-2013-058411, JP-A-5505656, and the like.

<base Generator  (B2)

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

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

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

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

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

As the base generator B2, there can be mentioned, for example, International Publication No. 2011/136074 pamphlet, Japanese Laid-Open Patent Publication No. 2012-193340, Japanese Laid-Open Patent Publication No. 2013-241548, Japanese Laid-Open Patent Publication No. 2013-241607, For example, Japanese Patent Publication No. 2014-097930, International Publication No. 2012/026400 pamphlet, Japanese Patent Publication No. 5406995, and the like.

[ Polymerizable  Compound (C)]

The composition for forming a water-trapping film used in the present invention preferably further contains a polymerizable compound (C). By containing the polymerizable compound (C) in the composition used in the present invention, for example, the crosslinking reactivity can be enhanced. The strength of the moisture-trapping film formed with this composition and the adhesion between the substrate and the organic EL layer can be improved.

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

The polymerizable compound (C) may be used alone or in combination of two or more.

As the polymerizable compound (C), for example, a compound having a cyclic ether group such as a compound having an epoxy group or a compound having an oxetanyl group; And a compound having a polymerizable double bond.

As the compound having an epoxy group, for example,

As the monofunctional epoxy compound, glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxypolyethylene glycol glycidyl ether, phenol Ethylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, allyl glycidyl ether, phenylglycidyl ether, p-methylphenyl glycidyl ether, Butylphenylglycidyl and the like;

As the polyfunctional epoxy compound,

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

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

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

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

As the compound having an oxetanyl group, for example,

As the monofunctional oxetane compound, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- Ethyl-3- (dodecyloxymethyl) oxetane, 3-ethyl-3- (octadecyloxymethyl) oxetane, 3- Methyl oxetane and the like;

As the polyfunctional oxetane compound, xylylene bisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetan-3-yl) methoxymethyl] -Ethyloxetane-3-yl) methoxy] methyl} oxetane, and 1,1,1-tris [(3-ethyloxetan-3-yl) methoxymethyl] propane.

As the compound having a cyclic ether group, from the viewpoint of enhancing the crosslinking reactivity, a compound having an epoxy group is preferable, a polyfunctional epoxy compound is more preferable, and a polyglycidyl ether of a polyhydric alcohol, 3,4-epoxycyclohexyl Particularly preferred are compounds having a functional group and polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate .

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

Among these compounds, polyfunctional (meth) acrylate compounds are preferable, polyfunctional methacrylate compounds are more preferable, and polyethylene glycol dimethacrylate, poly Propylene glycol dimethacrylate is more preferable, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferable.

When the polymerizable compound (C) is used in the composition used in the present invention, its content is preferably 10 to 3,000 parts by mass, more preferably 50 to 2,000 parts by mass, per 100 parts by mass of the component (A). When the content of the polymerizable compound (C) is within the above range, adhesion of the water-trapping film to the substrate or the organic EL layer can be effectively increased.

[ Radical  polymerization Initiator  (D)]

The composition for forming a water-trapping film used in the present invention may further contain a radical polymerization initiator (D). (Iii-1-1) and metal hydroxide (iii-1-2) formed by the hydrolysis reaction represented by the above-mentioned chemical reaction formula by containing the initiator (D) ) Is efficiently immobilized in the moisture trapping film formed of the composition, and it is easy to stay.

The initiator (D) may be used alone, or two or more thereof may be used in combination.

Examples of the initiator (D) include thermal radical polymerization initiators such as azo compounds and peroxides; Based compound, a benzophenone-based compound, an? -Diketone-based compound, a polynuclear quinone-based compound, a thioxanthone-based compound, a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, an O-acyloxime compound, , An acylphosphine oxide-based compound, and an imidosulfonate-based compound.

When the radical polymerization initiator (D) is used in the composition used in the present invention, its content is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the component (A). By setting the content of the initiator (D) within the above range, the desired radical polymerization reaction can be promptly advanced.

[Other optional ingredients]

The composition used in the present invention may further contain other optional components. Examples of other arbitrary components include silicone rubbers, silicone oils, and diene polymers in order to alleviate the stress of the formed moisture trapping film. In addition, a silane coupling agent, a surfactant, a pigment such as carbon black, a dye, an antioxidant, a stabilizer, a heat-resistant filler, a carbodiimide compound and other additives may be mentioned.

As the silane coupling agent, for example, KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. In addition, JP-A 2006-171670, JP-A 2006-184908, JP-A- May be mentioned. Examples of the surfactant include the compounds described in JP-A-2012-226181 and JP-A-2013-23414.

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, and also known in International Patent Publication Nos. 2004-055064, 04-224813, 09-095507, 2004-197107 And JP-A-2007-254692.

Examples of the carbodiimide compound include polycarbodiimide, and also include compounds described in JP-A-05-178954, JP-A-09-124582, JP-A-10-067978 , Japanese Unexamined Patent Application Publication No. 2007-138080, International Publication No. 2008-081230, and International Publication No. 2010-071211 pamphlet.

[Method for preparing composition for forming water-trapping film]

The composition for forming a water-trapping film used in the present invention is prepared by mixing the component (A) and the component (B), and mixing the components (C), (D) can do.

The composition used in the present invention can be suitably used as a moisture-trapping film for producing an organic EL device in which moisture may deteriorate its properties. For example, the moisture-trapping film formed by irradiating and / or heating a coating film composed of the above composition can absorb moisture in the element for a long period of time. It is also possible to re-express the water trapping ability of the composition by irradiating and / or heating the moisture trapping film disposed in the organic EL device.

(Example)

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of examples and the like, &quot; part &quot; means &quot; part by mass &quot; unless otherwise stated.

[ ^One H- NMR Measurement]

&Lt; ¹ &gt; H-NMR was measured at 25 DEG C using a nuclear magnetic resonance apparatus (JNM-ECS400 (400 MHz), manufactured by JEOL).

[moisture Capture agent  (Synthesis of Compound (A1)

[ Synthetic example  1] Moisture Capture agent  ( AO -1) Synthesis of

To the reactor equipped with a stirrer, a condenser, a temperature controller and a solvent recovery device, 53.0 parts of methyl orthoformate, 80.0 parts of 2-butyl-2-ethyl-1,3-propanediol, 17.0 parts of pentaerythritol, 0.5 part of the aqueous solution was added thereto, and the resulting methanol was kept at about 85 占 폚 for 1 hour while distilling off the 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 trapping agent (AO-1) as a colorless transparent and viscous polyorthoester.

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

_{^{1 H-NMR (CDCl 3)}} ; (24H, m), delta 5.22 (4H, m), delta 1.10-1.60 (32H, m), delta 3.34-4.10 s).

[ Synthetic example  2] Moisture Capture agent  ( AO -2)

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

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

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

[ Synthetic example  3] Moisture Capture agent  ( AO -3)

50.0 parts of water trapping agent (AO-1) and 3.0 parts of t-butoxy potassium were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature control device and a solvent recovery device and stirred at 160 DEG C for 6 hours under a nitrogen atmosphere. Thereafter, 0.6 part of kyoward 600S (manufactured by Kyowakagaku Kogyo K.K.) as an alkali absorbent was added and the mixture was treated at 120 ° C for 1 hour. The reaction mixture was cooled to room temperature, and the adsorbent was filtered to obtain a colorless transparent, viscous A water entrapping agent (AO-3) was obtained as a polyorthoester.

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

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

[ Synthetic example  4] Moisture Capture agent  ( AO -4)

63.0 parts of methyl orthoformate, 55.0 parts of glycerin, 20.0 parts of pentaerythritol and 0.5 part of a 90 wt% formic acid aqueous solution were placed in a reaction apparatus equipped with a stirrer, a condenser, a temperature control device and a solvent recovery device. Methanol Was kept at about 85 캜 for 1 hour while distilling off. Thereafter, the temperature was raised to 175 ° C over 2 hours to recover 57.0 parts of methanol, and the mixture was concentrated under the conditions of 175 ° C and 300Pa to remove volatile components. As a colorless transparent and viscous polyorthoester, a water entrapping agent (AO-4) was obtained.

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

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

[Preparation of composition for forming moisture trapping film]

(A) (component (A)), the acid generator (B1) (component (B)) and the polymerizable compound (C) (component (B)) used in preparing the water- C) is shown below.

<Component (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 Kasei Kogyo Co., Ltd.)

AS-2: 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

AC-1: Calcium oxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

<Component (B)>

B-1: CPI-210S (manufactured by SANA PRO)

(X = special negative ion)

&Lt; Component (C) &gt;

C-1: CELLOXIDE 2021P (manufactured by Daicel Corporation; 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate)

[ Preparation example  One]

23 parts of (AO-1) as the water capturing agent (A), 2 parts of (B-1) as the acid generator (B1) and 75 parts of the polymerizable compound (C) The mixture was thoroughly mixed using a stirrer (Awatore Rentero, Shin-Kisa Co.). Thereafter, defoaming was carried out under vacuum to prepare a composition for forming a moisture-trapping film.

[ Preparation example  2 to 8 and comparison Preparation example  1-2]

A composition for forming a moisture-trapping film was prepared in the same manner as in Preparation Example 1 except that the ingredients and formulation amounts shown in Table 1 were used in Preparation Example 1.

[abandonment EL  Manufacturing of device]

On a glass substrate (Asahi Glass Co., Ltd.) having an ITO film having a thickness of 15 nm and a thickness of 2 mm formed on a glass plate having a length of 25 mm and a thickness of 0.7 mm, poly (3,4) ethylenedioxy Spin coating was carried out at 3000 rpm for 50 seconds to form a hole injection layer having a film thickness of 50 nm, and then a high purity nitrogen was formed at 200 占 폚 Followed by heating and drying for 10 minutes. Here, PEDOT / PSS dissolved in pure water at a solid content of 0.1% by mass was used as a coating liquid for forming the hole injection layer. A 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated on the hole injection layer at 2000 rpm for 50 seconds to form a light emitting layer having a thickness of 70 nm, followed by baking at 60 캜 for 10 minutes. 10 nm of Ca was deposited on the light emitting layer at a deposition rate of 0.1 nm / sec under a pressure of 10 ^-5 Pa at a deposition rate of 0.1 nm / sec, and a deposition rate of 20 nm / sec was deposited thereon Al was laminated to 100 nm to form a cathode. Thus, an organic EL layer was formed on the glass substrate.

Subsequently, on the organic EL layer formed on the glass substrate, the moisture trapping film-forming composition was coated at a coating speed of 2 cm / sec using a bar coater "E-789" (Yoshimitsu Seikisha) having an interlaminar dimension of 100 μm To form a coating film having a thickness of 50 mu m. The film thickness of the coating film was measured by a depth gauge 547-251 (manufactured by Mitsutoyo Co., Ltd.). The resulting coating film was subjected to exposure using a PLA-501F exposure apparatus (ultra-high pressure mercury lamp, manufactured by Canon Inc.) so as to have an integrated irradiation amount of 30000 J / m 2 and then heated in a clean oven at 80 캜 for 1 hour, A moisture trapping film was formed as a cured product on the organic EL layer on the substrate.

Subsequently, a composition having the same composition as the composition for forming a water-trapping film obtained in Comparative Preparation Example 1 was applied to the periphery of the glass substrate on which the film formation was completed using a dispenser to form a 100 占 퐉 thick film . Subsequently, an opposing glass substrate having a length of 25 mm and a thickness of 0.7 mm was bonded to the glass substrate on which the film formation was completed using the vacuum bonding apparatus via the above-mentioned coating film. An ultrahigh pressure mercury lamp (intensity at 365 nm of 100 mW) For 30 seconds, and then heated at 80 占 폚 for 30 minutes to cure the coating film to form a sealing material.

Thus, an organic EL device was manufactured.

[evaluation]

The moisture-capturing film-forming composition, the cured product and the organic EL device were evaluated as follows.

<Adhesiveness>

Two glass pieces each having a thickness of 0.7 mm and a glass substrate cut to 25 mm x 75 mm were prepared. The composition for forming a moisture trapping film was applied to a central portion of one glass piece to form a coating film having a thickness of 100 mu m, and the two glass pieces were crossed in a cross shape to be adhered via the above coating film. The coating film was cured by exposure using a PLA-501F exposure machine (ultrahigh pressure mercury lamp, manufactured by Canon Inc.) so that the cumulative irradiation amount became 30000 J / m 2 and then heated in a clean oven at 80 캜 for 1 hour. The glass substrate was peeled up and down under the conditions 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 a size of 25 mm x 75 mm and the composition for forming a moisture trapping film was applied to a thickness of 100 m. Exposure was performed using a PLA-501F exposure apparatus (ultrahigh-pressure mercury lamp, manufactured by Canon Inc.) so that the cumulative irradiation dose was 30000 J / m 2, and then cured by heating at 80 ° C for 1 hour in a clean oven, To form a water-trapping film. The visible light transmittance (400 to 800 nm) before and after the humidity resistance test (85 DEG C, 85 RH%, 200 hours) was measured with a UV-VIS measuring device (Nippon Bunko V650) and a glass substrate as a reference.

<Moisture resistance test>

The ratio (%) of the dark spots to the surface area of the upper surface of the organic EL layer formed when the organic EL device obtained above was energized for 500 hours under the conditions of 85 캜 and 85% RH was measured. When the ratio was 5% or less, it was judged that the moisture resistance was good, that is, the occurrence of dark spots was suppressed.

[Table 1]

10: substrate
20, 201: sealing material
30: sealing member
40: organic EL layer
50, 501, 510: moisture capture film
502, 503: Support member
100, 101, 200, 300, 400: Organic EL device

Claims (7)

A substrate;
An organic EL layer formed on the substrate,
An organic EL device having a sealing member,
In the sealing space of the organic EL device,
(A) a compound having a hydrolyzable structure, and
(B) at least one compound selected from the group consisting of an acid generator and a nucleating agent. The water-trapping film is formed by using a composition for forming a water-trapping film. The method according to claim 1,
Wherein 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 carbonic acid anhydride (A2) At least one compound selected from the group consisting of a compound represented by the formula (A3-1) and a compound represented by the formula (A3-2) (A3)
The compound (B) is an organic EL element which is an acid generator:

Wherein R ¹ to R ⁵ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or a group having 1 to 18 carbon atoms And 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 atoms to which they are bonded directly, and n is 0 or An integer of 1 to 18, and * represents a bonding position; In the formula (A1-2), R ¹ is a hydrogen atom or an organic group having 1 to 18 carbon atoms; Each R ⁸ is independently an organic group having 3 to 10 carbon atoms;

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

[In the formulas (A3-1) and (A3-2), X is a silicon atom, a titanium atom or a zirconium atom; R ¹ is an organic group having at least one group selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group and an isocyanate group, An alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group; R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, An oxyl group, a glycidoxy group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, or a mercapto group;
p is an integer from 0 to 6;
r is an integer of 0 to 2, and s is an integer of 1 to 30; 4. The method according to any one of claims 1 to 3,
The composition for forming a water-trapping film,
(C) a polymerizable compound. 4. The method according to any one of claims 1 to 3,
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. 4. The method according to any one of claims 1 to 3,
Wherein the moisture trapping film is disposed so as to be apart from the sealing member. (A) a compound having a hydrolyzable structure, and
(B) at least one compound selected from an acid generator and a base generator, wherein the moisture trapping film is formed using a composition for forming a water trapping film,
An organic EL device comprising: a substrate; an organic EL layer formed on the substrate; and a moisture trapping film disposed in an encapsulation space of the organic EL device having the encapsulation member.

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