WO2014021309A1

WO2014021309A1 - Water-collecting agent, and organic electronic device and organic el device each utilizing same

Info

Publication number: WO2014021309A1
Application number: PCT/JP2013/070593
Authority: WO
Inventors: 大樹田畑; 根本　友幸
Original assignee: 三菱樹脂株式会社
Priority date: 2012-07-30
Filing date: 2013-07-30
Publication date: 2014-02-06
Also published as: TW201412844A

Abstract

[Problem] To provide a resin composition which can be used as a water-collecting agent for an element that is susceptible to moisture or oxygen, e.g., an organic EL element, and which is transparent and therefore can be arranged on a light-emitting surface side without blocking out light, and from which any alcohol is not produced as a by-product. [Solution] A resin composition comprising at least one carboxylic acid anhydride and a non-reactive resin having no reactivity with a carboxylic acid anhydride group, wherein the content of the carboxylic acid anhydride group in the resin composition is 0.556 mmol/g or more and the total light transmittance of a product produced by molding the resin composition in a thickness of 100 μm is 80% or more.

Description

Water trapping agent, organic electronic device and organic EL device using the same

The present invention relates to a resin composition comprising a non-reactive resin having no reactivity with at least one carboxylic acid anhydride and a carboxylic acid anhydride group, a water catching agent using the resin composition, and the The present invention relates to an organic electronic device and an organic EL device using a water catching agent.

Conventionally, electronic devices (elements) using organic compounds have been developed. Organic electronic devices such as organic EL devices, organic TFT devices, organic solar cells, and electronic paper are devices that exhibit various functions by repeatedly injecting or extracting electrons and holes in an organic material. . That is, the device operating mechanism is to repeatedly perform the oxidation-reduction reaction of the organic material.

In particular, an organic EL element using electroluminescence (hereinafter referred to as EL) of an organic material is provided with an organic layer in which an organic charge transport layer or an organic light emitting layer is laminated between an anode and a cathode. It attracts attention as a light emitting element capable of high luminance light emission by voltage direct current drive. This organic EL element is expected as a flexible display because all materials can be composed of solid.

On the other hand, when the organic EL element is driven for a certain period, there is a problem that light emission characteristics such as light emission luminance, light emission efficiency, and light emission uniformity are significantly deteriorated as compared with the initial case. The causes of such deterioration of the light emission characteristics include oxidation of the electrode due to oxygen that has entered the organic EL element, oxidative decomposition of the organic material due to heat generation during driving, and the electrode due to moisture in the air that has entered the organic EL element. Examples thereof include oxidation and modification of organic substances. Furthermore, the interface of the structure peels off due to the influence of oxygen and moisture, the heat generation during driving and the environment during driving are high temperature, etc. Mechanical deterioration of the structure such as stress generated at the interface of the body and peeling of the interface can also be cited as a cause of the deterioration of the light emission characteristics.

In order to prevent such a problem, many techniques for sealing an organic EL element and suppressing contact with moisture and oxygen have been studied. For example, as shown in FIG. 1, a water catching agent 6 is used as a drying means for a pixel area in which organic EL elements including a transparent electrode 3, an organic functional layer 4, and a metal cathode electrode 5 are formed on a substrate 1. There is disclosed a method for preventing moisture from reaching the organic EL element by covering the inner wall with a sealing cap 2, filling the inside with nitrogen gas, and fixing to the substrate 1 with an adhesive 7 ( For example, see Patent Document 1). Moreover, the method of reducing the influence of oxygen by using an oxygen absorbent instead of a water catching agent is also disclosed (for example, refer patent document 2).

Various substances have been studied as the water catching agent. Among them, alkaline earth metal oxides such as barium oxide (BaO) and calcium oxide (CaO) physically adsorb water such as silica gel and zeolite. Unlike water trapping agents, it has been widely studied because it can be dried to a completely dry state by chemical adsorption of water, and there is no re-release of water in the operating temperature range.

However, these water scavengers react with water to produce highly corrosive hydroxides, so they are installed on the inner wall of the concave sealing cap 2 away from the

electrodes

3, 5 and the organic functional layer 4. Is done. This has the disadvantage that the element becomes thick. In addition, since these water capturing agent particles are opaque, they can be applied to a so-called bottom emission type display device in which display light is taken out from the substrate 1 side, but display light from the sealing cap 2 side opposite to the substrate 1. In the case of applying to a so-called top emission type display device, since the water capturing agent 4 prevents the transmission of display light, the water capturing agent 4 must be disposed so as not to cover the pixel area. There is a restriction that a new place must be provided.

Some proposals have been made to apply a water catching agent to such a top emission type display device. For example, it has hitherto been proposed to apply transparent and water-absorbing polymers such as polyvinyl alcohol and nylon as water-absorbing agents, but these polymers have the property of physically adsorbing water and are absolutely dry. Insufficient to dry to a state. In addition, in the organic EL element having the top emission structure, the particulate water-absorbing agent is disposed to such an extent that the light transmittance is not hindered (see Patent Document 3), and the particle size is smaller than the emission wavelength of the organic EL element. Although it has been proposed to use a plastic substrate in which a water-absorbing agent is dispersed (see Patent Document 4), in any case, there is a difficulty in arrangement method and transparency in the organic EL element, and practicality poor.

As a means for solving these problems, it has been disclosed to use a water-absorbing membrane with little visible light absorption (see Patent Document 5). This water capturing film can be formed by solvent coating a special moisture-reactive organometallic compound, and has sufficient transparency. However, when this water trapping film is applied to a flexible substrate, it is composed of a low-molecular compound, so that it lacks flexibility, and the compound after moisture absorption is further fragile. Moreover, since the water catching agent currently disclosed by patent document 5 has a mechanism which chemically capture | acquires water by hydrolysis of an organometallic compound, alcohol produces | generates by reacting with water, and this alcohol is organic EL. When the element is foamed due to local heat generation during start-up of the element, or when the evaporated compound aggregates on the element and no passivation film is provided, the organic compound is dissolved or the organic compound and the electrode There were problems such as penetration into the interface and erosion of the device.

As described above, most of the known technologies related to transparent water catching agents utilize hydrolysis of organometallic compounds, etc., and fundamentally solve the deterioration of physical properties due to low molecular weight and device defects due to by-product alcohol. However, it is not possible to obtain a transparent water catching agent.

Japanese Patent Laid-Open No. 9-148066 JP 7-169567 A JP 2001-357773 A JP 2002-56970 A JP 2003-142256 A JP 2007-191511 A

The present invention has been made in order to solve the above-described problems, and the object of the present invention is to use it as a water-absorbing agent for elements that are easily affected by moisture and oxygen such as organic EL elements. To provide a resin composition that is transparent, can be installed on the light emitting surface side without blocking light, and does not produce alcohol as a by-product, and to provide an organic EL element that maintains light emission characteristics over a long period of time is there.

As a result of earnestly examining a water capturing mechanism that does not by-produce alcohol by a chemical reaction with water without depending on hydrolysis of an organometallic compound, the present inventors have utilized a carboxylic acid anhydride having a specific structure, It was clarified that the water-capturing function and transparency were compatible, and alcohol was not produced as a by-product. Moreover, it discovered that a moldability could be provided, maintaining a water-capturing function by using non-reactive resin which has no reactivity with a carboxylic anhydride group.
In addition, the present inventors have found that a resin composition in which a carboxylic acid anhydride and a carbodiimide compound are used in combination is effective as a transparent water catching agent and can form a film by a solvent-free process. Furthermore, it discovered that the function as a water catching agent could be improved by making the abundance of a carboxylic acid anhydride and a carbodiimide compound within a specific range.
Furthermore, the resin composition of the present invention has a performance equal to or better than that of conventionally used organometallic water catching agents, and is used as a water catching agent for organic electronic devices, particularly top emission type organic EL elements. It was confirmed that it can be suitably used.

That is, the gist of the present invention is as follows.
[1] A resin composition comprising at least one carboxylic anhydride and a non-reactive resin having no reactivity with a carboxylic anhydride group, wherein the carboxylic anhydride group in the resin composition The said resin composition whose content is 0.556 mmol / g or more and whose total light transmittance is 80% or more when this resin composition is shape | molded by 100 micrometers in thickness.
[2] The resin composition according to [1], wherein the carboxylic acid anhydride is an alicyclic carboxylic acid anhydride.
[3] At least one carboxylic acid anhydride and a carbodiimide compound are contained, and the contents of all carboxylic acid anhydrides and all carbodiimide compounds satisfy the following relational expressions (1) to (3): The resin composition according to [1] or [2], wherein the amount of water captured at 90% Rh is 1% by weight or more.
(1) A ≧ α / 18
(2) B = Anβ / α (provided that 0.25 ≦ n ≦ 2.5)
(3) A + B ≦ 100
(here,
A: Content (% by weight) of total carboxylic acid anhydride in the resin composition
B: Content (% by weight) of all carbodiimide compounds in the resin composition
α: acid anhydride equivalent of all carboxylic acid anhydrides (g / eq)
β: carbodiimide equivalent of all carbodiimide compounds (g / eq)
Indicates. )
[4] A water capturing agent using the resin composition according to any one of [1] to [3].
[5] The water catching agent according to [4], including a mixture of carboxylic acid anhydrides composed of two or more kinds of carboxylic acid anhydrides.
[6] Non-reactive resin is selected from poly (meth) acrylate, urethane (meth) acrylate and its cured product, polyester, polyvinyl ester, polyolefin, polystyrene, epoxy resin cured product, polycarbodiimide and copolymers thereof. The water catching agent according to [4] or [5], which is any one or more selected.
[7] A laminated film having a layer containing the water catching agent according to any one of [4] to [6].
[8] An organic electronic device having a layer containing the water capturing agent according to any one of [4] to [6].
[9] An organic EL device using the water capturing agent according to any one of [4] to [6].
[10] An organic electronic device using the laminated film according to [7].
[11] An organic EL device using the laminated film according to [7].
It exists in

The resin composition of the present invention is transparent and has a large amount of water capture, does not by-produce alcohol by a chemical reaction with water, can be suitably applied to a top emission type display device, and is representative of organic EL elements. This contributes to extending the life of organic electronic devices.
In addition, the resin composition using the carboxylic acid anhydride and the carbodiimide compound of the present invention in combination is transparent and has a large water capture amount, does not produce gas or low molecular weight substances by chemical reaction with water, and is a film in a solvent-free process. It can be formed, can be suitably applied to a top emission type display device, and contributes to a long life of an organic electronic device typified by an organic EL element.

It is sectional drawing which shows typically the structure of this invention and the conventional organic EL element. It is sectional drawing which shows typically the structure of the organic EL element of this invention. It is sectional drawing which shows typically the structure of the organic EL element of this invention. It is an infrared absorption spectrum before and behind reaction of the resin composition of Example 11 and water.

Hereinafter, examples of embodiments of the present invention will be described, but the present invention is not limited to the embodiments described below.

One embodiment of the present invention is a resin composition comprising at least one carboxylic acid anhydride and a non-reactive resin that is not reactive with a carboxylic acid anhydride group, the carboxylic acid in the resin composition comprising This resin composition has an acid anhydride group content of 0.556 mmol / g or more and a total light transmittance of 80% or more when molded into a thickness of 100 μm (Embodiment 1).

Resin Composition of Embodiment 1 The resin composition of Embodiment 1 of the present invention (hereinafter also referred to as “resin composition of the present invention”) contains two or more kinds of carboxylic acid anhydrides and non-reactive resins, respectively. You can leave.

<Carboxylic anhydride>
The resin composition of the present invention contains one or more carboxylic acid anhydrides. Although the water collection capacity required for practical use differs depending on the application, the water capture capacity is preferably 1% by weight or more, and more preferably 2% by weight or more. If the water-capturing capacity is large, a sufficiently superior effect can be expressed over the physical adsorption type water-capturing agent.
Since the carboxylic anhydride group reacts 1: 1 with water molecules, 18 g of water can be captured per 1 mol of the carboxylic anhydride group. Therefore, if the content of carboxylic acid anhydride in the resin composition is 0.556 mmol / g, it can be said that the resin composition can capture about 1% by weight of water.
That is, in order to satisfy the water catching capacity, the content of carboxylic acid anhydride groups in the resin composition is preferably 0.556 mmol / g or more, and more preferably 1.11 mmol / g or more.

The content of carboxylic acid anhydride can be determined by dissolving the resin composition in a solvent and titrating with triethylamine or the like, as described in JP 2010-030942 A. However, if it is before the reaction with water, it can be theoretically determined from the amount of carboxylic anhydride added.

Although the total amount of all carboxylic acid anhydrides depends on the molecular weight of the carboxylic acid anhydride, it is preferably 10% by weight or more based on the total weight of the resin composition. The type of the carboxylic acid anhydride is an alicyclic carboxylic acid. Anhydrides are preferred. By using the alicyclic carboxylic acid anhydride, the molecular weight is not lowered by reaction with water. Moreover, it can be set as the transparent resin composition with less coloring than aromatic carboxylic acid anhydride.
As the alicyclic carboxylic acid anhydride, a maleic anhydride copolymer and a maleic anhydride derivative are preferable, and a Diels-Alder addition reaction product of maleic anhydride and various dienes is particularly preferable. Examples of the Diels-Alder addition reaction product of maleic anhydride and various dienes include alicyclic carboxylic acid anhydrides represented by the following chemical formulas (1), (2), and (3). Usually, the Diels-Alder addition reaction product of maleic anhydride and various dienes is required to have a double bond, but from the viewpoint of preventing coloring and reverse Diels-Alder reaction, hydrogenation, radical polymerization, You may change a double bond into a single bond by thiol reaction etc.

(Wherein R ₁ and R ₂ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a sulfur atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, a carboxyl group, an alkoxy group) Group, a thioalkoxy group, an acylurea group to which an organic group is bonded, an alkoxycarbonyl group, an acyl group, or an acyloxy group, R ₁ and R ₂ may be bonded to each other to form a double bond, (A cyclic acid anhydride group may be formed.)

(Wherein R ₁ and R ₂ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, a sulfur atom, an alkyl group, an aryl group, a cycloalkyl group, a heterocyclic group, a carboxyl group, an alkoxy group) Group, a thioalkoxy group, an acylurea group to which an organic group is bonded, an alkoxycarbonyl group, an acyl group, or an acyloxy group, R ₁ and R ₂ may be bonded to each other to form a double bond; (A cyclic acid anhydride group may be formed.)

Examples of alicyclic carboxylic acid anhydrides of chemical formulas (1), (2), and (3) that are readily available include hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, Endomethylenetetrahydrophthalic anhydride, Methylendomethylenetetrahydrophthalic anhydride, Methylbutethenyltetrahydrophthalic anhydride, Cyclohexanetetracarboxylic anhydride, Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid Acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexanetricarboxylic acid anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic acid anhydride And bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetra Carboxylic acid dianhydride.

The resin composition of the present invention preferably contains an alicyclic carboxylic anhydride, but contains an aromatic and / or aliphatic carboxylic anhydride that is not alicyclic as long as the physical properties thereof are not impaired. Is possible.

Since the water-capacitance capacity of the carboxylic acid anhydride affects the acid anhydride equivalent (g / eq) of the carboxylic acid anhydride, the carboxylic acid anhydride has a plurality of carboxylic acid anhydride groups per molecule. Also good.
The smaller the value of the acid anhydride equivalent (g / eq) of the carboxylic acid anhydride, the greater the amount of moisture that can be captured per weight. Therefore, from the viewpoint of increasing the amount of water captured, it is preferable that the acid anhydride equivalent (g / eq) is small. On the other hand, from the viewpoint of increasing compatibility with other components in the resin composition, it is preferable to use a carboxylic acid anhydride having a large acid anhydride equivalent (g / eq), that is, a large molecular weight. In the present invention, the acid anhydride equivalent range is preferably 100 to 2000 g / eq, more preferably 120 to 1000 g / eq.

<Thiol compound>
The resin composition of the present invention preferably contains a thiol compound, and particularly effective in combination with an acid anhydride having a double bond. The mercapto group of the thiol compound undergoes an addition reaction with the double bond of the acid anhydride. Thus, the reverse Diels-Alder reaction of the carboxylic acid anhydride can be prevented by changing the double bond to a single bond, and the volatilization and bleed out of the carboxylic acid anhydride can be suppressed by increasing the molecular weight.
Although the thiol compound may be monofunctional, a polyfunctional thiol compound may be used. When a monofunctional thiol compound is used, the molecular weight of the carboxylic acid anhydride can be increased without curing. On the other hand, when a polyfunctional thiol compound is used, since the content of the thiol compound can be reduced, the content of the carboxylic acid anhydride can be increased.
The mercapto group of the thiol compound may be primary or secondary, and is selected in consideration of reactivity, pot life, handling properties, and economic efficiency. In general, the primary thiol compound is more reactive than the secondary, and the secondary thiol compound is superior in pot life than the primary.
Preferred examples of thiol compounds used in the resin composition of the present invention, which are easily available, include β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto Propionate), trimethylolpropane tris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), di Antaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) SC Organic Chemical Co., Ltd., grade 2 can be obtained from Showa Denko Co., Ltd.
In addition to the above, methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, , 2-cyclohexanedithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, Bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptomethylthio) methane Bis (2-mercaptoethylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3- Bis (2-mercaptoethylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercapto Propylthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7- Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,1 Dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2 -Bis (mercaptomethylthio) ethyl) -1,3-dithietane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5- Aliphatic thiol compounds such as dimercapto-1,4-dithiane;
Ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), diethylene glycol (2-mercaptoacetate), diethylene glycol (3-mercaptopropionate), 2,3-dimercapto-1-propanol ( 3-mercaptopropionate), 3-mercapto-1,2-propanediol bis (2-mercaptoacetate), 3-mercapto-1,2-propanediol di (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate) , Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol (3-mercaptopropionate), glycerol tris (2-mercaptoacetate), glycerol tris (3-mercaptopropionate), 1,4-cyclohexanediol bis ( 2-mercaptoacetate), 1,4-cyclohexanediol bis (3-mercaptopropionate), hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide ( 2-mercaptoacetate), hydroxyethyl sulfide (3-mercaptopropionate), hydroxymethyl disulfide (2-mercaptoacetate), hydroxymethyldisulfur I de (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester) and the like, aliphatic thiol compound containing an ester bond;
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2- Bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1, 2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 2,5-tolu Dithiol, 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3,4-tetramercaptobenzene, , 2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) ) Benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 2,4,5-tetrakis (mercaptoethyl) benzene, 2,2'-dimercaptobiphenyl, 4,4'- Aromatic thiol compounds such as dimercaptobiphenyl can be used.

<Non-reactive resin>
The resin composition of the present invention contains one or more non-reactive resins that are not reactive with carboxylic anhydride groups, and the total amount of all the non-reactive resins is preferably 11 to 90% by weight, More preferably, it is 30 to 80% by weight. When the non-reactive resin is 90% by weight or less, the content of the carboxylic acid anhydride is not relatively decreased, and a sufficient water capturing function can be ensured. Moreover, it can prevent predominately that a moldability deteriorates by making a non-reactive resin into 11 weight% or more.

As such a non-reactive resin, a resin that does not contain an active hydrogen group as a main component, for example, an amino group, an imino group, an isocyanate group, or a resin that does not have a hydroxyl group is preferable. Specifically, poly (meth) acrylate, Examples include urethane (meth) acrylate and its cured product, polyester, end-capped polyether, polyvinyl ester, polyolefin, polystyrene, epoxy resin cured product, polycarbodiimide, and copolymers thereof.

Alternatively, a non-reactive resin may be obtained by reacting a functional group of a resin reactive with a carboxylic anhydride group in situ (in the composition). Examples of such a non-reactive resin include a cured epoxy resin. That is, the resin composition of the present invention can be obtained by curing a curable epoxy resin containing a large excess of carboxylic acid anhydride.

<Third component>
The resin composition of the present invention may contain a third component in addition to the above components. As this third component, from the viewpoint of maintaining the water-capturing function of the resin composition, it is preferable that the main component does not contain an active hydrogen group (for example, amino group, imino group, isocyanate group, hydroxyl group), but the resin composition A component containing an active hydrogen group can be added as long as the carboxylic acid anhydride group remains in the range where 0.556 mmol / g or more remains.

The third component that is preferably contained in the resin composition of the present invention includes an organometallic compound that has been conventionally known as a water-absorbing agent. As such an organometallic compound, compounds represented by the following formulas (4), (5), (6) and (7) are preferable. The content of these organometallic compounds in the resin composition is preferably 30% by weight or less. If it is 30% by weight or less, the water-absorbing agent has good flexibility and can prevent the occurrence of defects such as cracks.

(Wherein R1 to Rn are each independently an organic group containing an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, a heterocyclic group, or an acyl group, and M is a trivalent or tetravalent group. Indicates a metal atom.)

(Wherein R ₁ to R ₃ each independently represents an organic group containing an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, a heterocyclic group, or an acyl group, and M represents a trivalent metal. Indicates an atom.)

(Wherein R ₁ to R ₃ and R ₅ each independently represents an organic group containing an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, a heterocyclic group or an acyl group, and M is 3 Represents a valent metal atom.)

(Wherein R ₁ , R ₃ and R ₄ each independently represents an organic group containing an alkyl group having 1 or more carbon atoms, an aryl group, a cycloalkyl group, a heterocyclic group or an acyl group; Represents a valent metal atom.)

Furthermore, examples of the inorganic compound preferably contained in the resin composition of the present invention include highly refractive particles having a particle size of 100 nm or less. By dispersing highly refractive particles having a particle diameter of 100 nm or less in the resin composition, it is possible to increase the refractive index of the resin composition without impairing transparency. By increasing the refractive index of the resin composition, the light extraction property can be improved in the organic EL. Examples of such highly refractive particles include zirconium oxide and tin oxide, and organosols in which these are dispersed in an organic solvent are commercially available.

Moreover, a catalyst can be mentioned as a 3rd component preferably contained in the resin composition of this invention. By adding a catalyst, the reaction between the carboxylic acid anhydride and water can be promoted. Examples of the catalyst preferably used in the resin composition of the present invention include pyridines such as quaternary phosphonium salts, quaternary ammonium salts, tertiary amines, DMAP (N, N-dimethyl-4-aminopyridine), DBU ( Amidines such as 1,8-diazabicyclo (5,4,0) undec-7-ene) and DBN (1,5-diazabicyclo (4,3,0) non-5-ene) and derivatives thereof, imidazoles, Examples include triazoles, tetrazoles, and pyrazoles. However, it is not limited to these as long as it has catalytic activity and is not colored.
In particular, DMAP, DBN, DBU and derivatives and salts thereof are more preferable because they exhibit high catalytic activity even with a small amount of addition. Among them, DBU salts and DBU derivative salts are sold as U-CAT series by Sun Apro Co., Ltd. and are easily available.
In this invention, said catalyst may be used independently or may use 2 or more types together.

Resin composition of Embodiment 2 Another embodiment (Embodiment 2) of the present invention contains at least one carboxylic acid anhydride and a carbodiimide compound, and contains all carboxylic acid anhydrides and all carbodiimide compounds. A resin composition satisfying the following relational expressions (1) to (3) and having an amount of water captured at 40 ° C. and 90% Rh of 1% by weight or more.
(1) A ≧ α / 18
(2) B = Anβ / α (provided that 0.25 ≦ n ≦ 2.5)
(3) A + B ≦ 100
(here,
A: Content (% by weight) of total carboxylic acid anhydride in the resin composition
B: Content (% by weight) of all carbodiimide compounds in the resin composition
α: acid anhydride equivalent of all carboxylic acid anhydrides (g / eq)
β: carbodiimide equivalent of all carbodiimide compounds (g / eq)
Indicates. )

As the carboxylic acid anhydride in the resin composition of Embodiment 2 of the present invention, an alicyclic carboxylic acid anhydride is preferable. As the alicyclic carboxylic acid anhydride, it is preferable to use the alicyclic carboxylic acid anhydrides represented by the chemical formulas (1), (2), and (3).
By using the alicyclic carboxylic acid anhydride, the molecular weight is not lowered by reaction with water. Moreover, it can be set as the transparent resin composition with less coloring than aromatic carboxylic acid anhydride.

In the resin composition of Embodiment 2 of the present invention, the content of carboxylic anhydride groups in the resin composition is preferably 0.556 mmol / g or more, and the total amount of all carboxylic anhydrides is the total weight of the resin composition It is preferable that it is 10 weight% or more with respect to.

The resin composition of Embodiment 2 of the present invention preferably contains an alicyclic carboxylic acid anhydride, but is not an alicyclic aromatic and / or aliphatic carboxylic acid anhydride as long as its physical properties are not impaired. It is possible to include objects.

<Carbodiimide compound>
The carbodiimide compound is not particularly limited, but polycarbodiimide having a high molecular weight and relatively low toxicity is preferable. Examples of commercially available polycarbodiimides include Stabaxol (trade name) manufactured by Rhein Chemie and Carbodilite (trade name) manufactured by Nisshinbo Chemical. Among them, those that do not contain aromatics in the structure and that are less colored are preferable, and polycarbodiimides that have a low content of isocyanate groups and are less likely to react with water to generate carbon dioxide are preferable. Examples of such polycarbodiimide include carbodilite HMV-15CA, HMV-8CA, V-02-L2B, V-04K, V-09, V-02B, AD-5004, and the like.

In addition, by using polycarbodiimide having a hydrophilic structure introduced, it is possible to improve the adsorption of water vapor to the resin composition and the diffusion of water vapor inside the resin composition, resulting in an increase in water capture efficiency. be able to. Carbodilite V-02B, V-02-L2B, and V-04K are commercially available as polycarbodiimides having such a hydrophilic structure introduced.

As the carbodiimide equivalent (g / eq) of the carbodiimide compound is smaller, the amount of carboxylic acid per weight can be increased. Therefore, from the viewpoint of increasing the trapping amount, it is preferable that the carbodiimide equivalent is small. On the other hand, it is preferable to use a carbodiimide compound having a large carbodiimide equivalent from the viewpoint of improving compatibility in the resin composition and imparting functions such as hydrophilization. The range of carbodiimide equivalent is preferably 150 to 2000 g / eq, more preferably 200 to 1000 g / eq.

<Carbonic anhydride and carbodiimide compound content and relationship>
The resin composition of Embodiment 2 of the present invention can be expected to have a beneficial effect as compared with the case of only the carboxylic acid anhydride by containing both the carboxylic acid anhydride and the carbodiimide compound. For example, since the carbodiimide group removes carboxylic acid, which is the reaction product of water and carboxylic anhydride, by the addition reaction, the reaction is accelerated and the water is re-released compared to the system using carboxylic anhydride alone. Tend to occur less easily. Also, some types of carboxylic acid anhydrides produce carboxylic acid crystals after reaction with water, but they prevent the formation and / or growth of carboxylic acid crystals and maintain transparency even after water capture. I can do it.

In order to obtain these effects, the contents of all carboxylic acid anhydrides and all carbodiimide compounds preferably satisfy the following relational expressions (1) to (3).
(1) A ≧ α / 18
(2) B = Anβ / α (provided that 0.25 ≦ n ≦ 2.5)
(3) A + B ≦ 100
(here,
A: Content (% by weight) of total carboxylic acid anhydride in the resin composition
B: Content (% by weight) of all carbodiimide compounds in the resin composition
α: acid anhydride equivalent of all carboxylic acid anhydrides (g / eq)
β: carbodiimide equivalent of all carbodiimide compounds (g / eq)
Indicates. )

That is, the content (% by weight) of the total carboxylic acid anhydride in the resin composition needs to be an amount obtained by dividing at least the acid anhydride equivalent (g / eq) by 18 which is the molecular weight of water. In the resin composition, the content (% by weight) of the total carbodiimide compound is such that the carbodiimide group is n times, that is, between 0.25 and 2 times the acid anhydride group. Is preferably adjusted. The carboxylic acid anhydride and the carbodiimide compound need to be blended in consideration of other components. As described above, 0.25 ≦ n ≦ 2.5 is preferable, but 0.4 ≦ n ≦ 2.0 is more preferable, and 0.5 ≦ n ≦ 1.8 is more preferable.

<Third component>
In addition to the above compounds (carboxylic acid anhydride and carbodiimide compound), the resin composition of Embodiment 2 of the present invention is within a range in which the amount of water captured by the resin composition is maintained at 1% by weight or more. May be included. Examples of the third component include resins other than the above compounds, catalysts, inorganic compounds, and the like. From the viewpoint of maintaining the water capturing function of the resin composition, the third component preferably does not contain an active hydrogen group (for example, an amino group, an imino group, an isocyanate group, or a hydroxyl group), but the amount of water captured by the resin composition is 1 A component containing an active hydrogen group can also be added as long as it is within a range where the weight percent is maintained.

The resin preferably contained in the resin composition of Embodiment 2 of the present invention may be a thermoplastic resin, a heat and / or energy ray curable resin, (meth) acrylate and its cured product, urethane (meth) acrylate. And its cured product, epoxy resin cured product, polyvinyl ester and its copolymer, polyolefin and its copolymer, polyester and its copolymer. The (meth) acrylate may be a monomer or an oligomer, and can impart UV curability when used in combination with a photopolymerization initiator. The content of these resins in the resin composition is preferably 60% by weight or less. When the amount is 60% by weight or less, the content of the carboxylic acid anhydride is not relatively decreased, and a sufficient water capturing function can be expected.

Further, as the third component preferably contained in the resin composition of Embodiment 2 of the present invention, an organometallic compound known as a water catching agent can be exemplified. As such an organometallic compound, compounds represented by the above formulas (4), (5), (6) and (7) are preferable. The content of these organometallic compounds in the resin composition is preferably 30% by weight or less. If it is 30% by weight or less, the flexibility of the resin composition after catching water is good, and the occurrence of defects such as cracks can be prevented.

In addition, examples of the inorganic compound that is preferably included in the resin composition of Embodiment 2 of the present invention include highly refractive particles having a particle diameter of 100 nm or less. By dispersing and arranging highly refractive particles having a particle diameter of 100 nm or less in the resin composition, it is possible to increase the refractive index of the resin composition without impairing transparency. The light extraction property can be improved by increasing the refractive index of the resin composition. Examples of such highly refractive particles include zirconium oxide and tin oxide, and organosols in which these are dispersed in an organic solvent are commercially available.

Furthermore, a catalyst that promotes the reaction between the carboxylic acid anhydride and water can be added as a third component to the resin composition of Embodiment 2 of the present invention. In the resin composition of Embodiment 2 of the present invention, the catalyst preferably used in the resin composition of Embodiment 1 of the present invention described above can be used in the same manner.

The resin composition of Embodiment 2 of the present invention is characterized in that the amount of water captured under the conditions of 40 ° C. and 90% Rh is 1% by weight or more. Here, the amount of water captured can be measured by the following method, for example. The resin composition is applied to an aluminum plate and the like, and the weight is measured to obtain an accurate weight (A) of the resin composition applied to the aluminum plate. Next, 40 ° C. and 90% until there is no change in weight. It is allowed to react sufficiently with water by leaving it in a constant temperature and humidity chamber of Rh. (React until the infrared absorption peaks (1785 cm ⁻¹ and 1862 cm ⁻¹ ) of the acid anhydride group of the resin composition disappear.) After confirming the reaction with water, before and after leaving in a constant temperature and humidity chamber The increased weight (B) is obtained and immediately dried until there is no weight change with dry air, and the weight (C) of the physically adsorbed water is obtained from the weight change before and after drying. And the amount of water captured (the amount of water captured by the reaction) is determined by the following equation.
Amount of captured water = ((B) − (C)) / (A) × 100 (% by weight)

<Form>
The resin compositions of

Embodiments

1 and 2 of the present invention may be in any form of liquid, particulate, sheet, or plate, and in the case of a sheet or plate, they may be laminated with other transparent materials. good. In the case of a particulate form, it can be arbitrarily selected as long as the transparency is not impaired, and generally 1 to 1000 nm is preferable.
The total light transmittance when the resin compositions of

Embodiments

1 and 2 of the present invention are molded to a thickness of 100 μm is preferably 80% or more.

<How to use>
The resin composition of the present invention can be suitably used as a water catching agent, and the water catching agent of the present invention can be applied to an element that is susceptible to moisture such as an organic EL element.
Since the water-absorbing agent of the present invention is transparent, it can be disposed on the light emitting surface and light receiving surface side of the element without blocking light. In addition, the water catching agent of the present invention is a laminated film in which a passive water vapor barrier film is arranged on the front and back (that is, a passive barrier / active barrier / passive barrier configuration), thereby reducing the water vapor transmission breakthrough time of the film. You can make it bigger.

Moreover, since the water-absorbing agent of the present invention is transparent, it can be used as a laminate for various optical elements. That is, another embodiment of the present invention is a laminate having a layer containing the water capturing agent. As described above, the water-absorbing agent of the present invention can capture moisture, and thus the laminate also exhibits hygroscopicity.

Furthermore, still another embodiment of the present invention is an organic EL device in which the water-absorbing agent is disposed as a drying means. The configuration of the organic EL element can be the same as that of the conventional organic EL element shown in FIG. 1, that is, the organic functional layer 4 made of an organic material is sandwiched between a pair of

electrodes

3 and 5 facing each other. A laminate cap, a sealing cap 2 such as an airtight container for containing the laminate and blocking outside air, and a drying means 6 disposed in the airtight container. It is formed from a water catching agent. Since this water-absorbing agent is transparent, there is no restriction on the position where the drying means 6 is arranged. Therefore, a film obtained by applying a water-absorbing agent to a water-blocking plastic film or the like is used as the drying means. As shown, the coating may be applied directly over the electrode 5. FIG. 2 shows a mode in which the sealing cap 2 is a plastic film, and a water catching agent is applied as a drying means 6 to the plastic film. Alternatively, as shown in FIG. 3, the drying means 6 may be arranged so as to cover the

electrodes

3 and 5 and the organic functional layer 4 on the substrate 1 and further covered with a sealing adhesive 7. Good.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Resin Composition of Embodiment 1]
<Example 1>
Under a nitrogen atmosphere, 3 g of Rikacid MH-700 (trade name of Shin Nippon Rika Co., Ltd., 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30 mixture, acid anhydride equivalent 161 g / eq) And 7 g of NK oligo U-200PA (trade name, Shin-Nakamura Chemical Co., Ltd., urethane acrylate, molecular weight 2,700, 62,000 mPa · s / 40 ° C.) to obtain a resin composition. Here, the carboxylic acid anhydride is a mixture of two or more having a cyclohexane skeleton, the content of the carboxylic acid anhydride is 30% by weight, and the content of the carboxylic acid anhydride group is 1.86 mmol / g.

<Example 2>
The resin composition was obtained in the same manner as in Example 1 except that the ricacid MH-700 was changed to 1 g and the NK oligo U-200PA was changed to 9 g. Here, the content of the carboxylic acid anhydride is 10% by weight, and the content of the carboxylic acid anhydride group is 0.62 mmol / g.

<Example 3>
Ricacid MH-700 was converted to Ricacid HNA-100 (trade name of Shin Nippon Rika Co., Ltd., methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2.1] heptane- The resin composition was obtained in the same manner as in Example 1, except that 2,3-dicarboxylic acid anhydride and acid anhydride equivalent of 180 g / eq) were used. Here, the carboxylic acid anhydride is a mixture of two or more having a norbornane skeleton. The content of carboxylic anhydride is 30% by weight, and the content of carboxylic anhydride groups is 1.67 mmol / g.

<Example 4>
1.5 g of Licacid HNA-100 and 1.5 g of hymic anhydride (manufactured by Hitachi Chemical Co., Ltd., norbornene skeleton, white crystals, acid anhydride equivalent 164 g / eq) are mixed, and the mixed carboxylic acid anhydride is mixed. Obtained. 3 g of the obtained mixed carboxylic acid anhydride was uniformly mixed with 7 g of NK oligo U-200PA to obtain a resin composition. Here, the carboxylic acid anhydride is a mixture of three types having a norbornane skeleton and a norbornene skeleton. The content of carboxylic acid anhydride is 30% by weight, and the content of carboxylic acid anhydride group is 1.74 mmol / g.

<Comparative Example 1>
Under a nitrogen atmosphere, 3 g of pyromellitic anhydride (aromatic carboxylic acid anhydride, acid anhydride equivalent 109 g / eq) was dissolved in 7 g of THF, mixed with 7 g of NK oligo U-200PA, and the THF was dried. To obtain a resin composition.

<Comparative Example 2>
A resin composition was obtained in the same manner as in Example 1 except that 10 g of NK oligo U-200PA was added without adding Ricacid MH-700.

<Comparative Example 3>
20.8 g of liquid OLEO (trade name of Hope Pharmaceutical Co., Ltd., 48% solution of aluminum oxide octylate oligomer), which is known as an organometallic water-absorbing agent, is dried under a nitrogen atmosphere to obtain a resin composition. Obtained.

<Measurement of water capture rate>
The above resin composition is measured in a glass petri dish so that the film thickness is 500 mm, and left in a constant temperature and humidity chamber at 40 ° C. and 90% Rh for 2 days. Asked. Subsequently, the water content (B) of the resin composition after treatment was obtained with a Karl Fischer moisture meter, and the water capture rate (% by weight) was obtained using (A)-(B) as the amount of water captured by the reaction.
The water capture rate was evaluated according to the following criteria.
(Evaluation criteria)
○: 1% by weight or more × less than 1% by weight

<Measurement of total light transmittance after catching water>
The total light transmittance of the above sample was measured and used as the total light transmittance after water capture.
Evaluation was made according to the following criteria.
(Evaluation criteria)
○: 80% or more ×: less than 80%

<State after catching water>
It observed visually and evaluated by the following references | standards.
(Evaluation criteria)
○: No defect is observed.
Δ: The crystal can be visually observed (within practical range).
X: Crystals are precipitated and whitened. Or a crack has occurred.

Table 1 shows the material ratios and various evaluation results of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3.

In Comparative Example 1 using an aromatic carboxylic acid anhydride, white crystals were deposited on the entire surface, so it was opaque and the amount of water captured was poor. However, in Examples 1 to 4, the transparency was maintained and the water capturing rate was good. Met. In particular, in Example 2, although the amount of the alicyclic carboxylic acid anhydride was 10% by weight, the water capturing rate was 1% by weight or more, and no crystal precipitation occurred. In particular, in Example 4, the crystallinity was suppressed by mixing two kinds of carboxylic acid anhydrides, the transparency was good, and the amount of water captured was excellent.

<Example 5>
NK Oligo U-200PA was changed to Carbodilite V-02B (trade name, Nisshinbo Chemical Co., Ltd., aqueous polycarbodiimide, carbodiimide equivalent 600 g / eq), and a resin composition was obtained in the same manner as in Example 1. Here, the content of carboxylic acid anhydride is 30% by weight, and the content of carboxylic acid anhydride group is 1.86 mmol / g.

<Example 6>
Under a nitrogen atmosphere, 3 g of Licacid HNA-100, 7 g of Evaflex EV150 (trade name of Mitsui DuPont Polychemical Co., Ltd., ethylene-vinyl acetate copolymer, vinyl acetate content 33%) and 10 g of The resin composition was obtained by dissolving and mixing in toluene and drying.

<Example 7>
3 g of Licacid HNA-100 was mixed with 14 g of Polyester LP-050 (trade name, Nippon Synthetic Chemical Co., Ltd., 50% polyester solution in toluene) and dried to obtain a resin composition.

<Example 8>
A resin composition was obtained in the same manner as in Example 5 except that Ricacid MH-700 was changed to 1 g and Carbodilite V-02B was changed to 9 g. Here, the content of the carboxylic acid anhydride is 10% by weight, and the content of the carboxylic acid anhydride group is 0.62 mmol / g.

<Example 9>
A resin composition was obtained in the same manner as in Example 5 except that Ricacid MH-700 was changed to 5 g and Carbodilite V-02B was changed to 5 g. Here, the content of carboxylic anhydride is 50% by weight, and the content of carboxylic anhydride group is 3.11 mmol / g.

<Comparative example 4>
A resin composition was obtained in the same manner as in Example 5 except that Ricacid MH-700 was changed to 0.5 g and Carbodilite V-02B was changed to 9.5 g. Here, the content of the carboxylic acid anhydride is 5% by weight, and the content of the carboxylic acid anhydride group is 0.31 mmol / g.

Table 2 shows the material ratios and various evaluation results of the resin compositions of Examples 5 to 9 and Comparative Example 4.

Examples 5 to 7 show that polycarbodiimide, polyvinyl ester, polyolefin, and polyester can be used as non-reactive resins in addition to (meth) acrylate. Moreover, from Examples 5, 8, 9 and Comparative Example 4, the water content of 1% by weight or more was expressed because the resin composition having a carboxylic acid anhydride group content greater than 0.556 mmol / g. Only.

[Resin Composition of Embodiment 2]
<Example 10>
Under a nitrogen atmosphere, 5.18 g of Rikacid MH-700 (trade name of Shin Nippon Rika Co., Ltd., 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30 mixture, acid anhydride equivalent 161 g / eq ) Was mixed with 4.82 g of Carbodilite V-02B (trade name, Nisshinbo Chemical Co., Ltd., hydrophilic polycarbodiimide, carbodiimide equivalent 600 g / eq) to obtain a transparent resin composition. The content of each material satisfies the relational expressions (1) to (3), and n = 0.25.

<Example 11>
Under a nitrogen atmosphere, 3.492 g of Licacid MH-700 was mixed with 6.508 g of Carbodilite V-02B (trade name, Nisshinbo Chemical Co., Ltd., hydrophilic polycarbodiimide, carbodiimide equivalent 600 g / eq), and transparent. A resin composition was obtained. The content of each material satisfies the relational expressions (1) to (3), and n = 0.5.

<Example 12>
Under a nitrogen atmosphere, 3.750 g of Rikacid HNA-100 (trade name, Shinnihon Rika Co., Ltd., methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] Heptane-2,3-dicarboxylic acid anhydride, acid anhydride equivalent 180 g / eq) was mixed with 6.250 g of carbodilite V-02B to obtain a transparent resin composition. The content of each material satisfies all the relational expressions (1) to (3), and n = 0.5.

<Example 13>
Under a nitrogen atmosphere, 1.812 g of Ricacid MH-700 and 1.812 g of Ricacid HNA-100 were mixed with 6.376 g of Carbodilite V-02B to obtain a transparent resin composition. The content of each material satisfies all the relational expressions (1) to (3), and n = 0.5.

<Example 14>
Under a nitrogen atmosphere, 2.116 g of Ricacid MH-700 was mixed with 7.884 g of Carbodilite V-02B to obtain a transparent resin composition. The content of each material satisfies all the relational expressions (1) to (3), and n = 1.0.

<Example 15>
Under a nitrogen atmosphere, 1.183 g of Ricacid MH-700 was mixed with 8.817 g of Carbodilite V-02B to obtain a transparent resin composition. The content of each material satisfies all the relational expressions (1) to (3), and n = 2.0.

<Comparative Example 5>
Under a nitrogen atmosphere, 7.29 g of Licacid MH-700 was mixed with 2.71 g of Carbodilite V-02B to obtain a transparent resin composition. n = 0.1, and the content of each material does not satisfy all the relational expressions (1) to (3).

<Comparative Example 6>
Under a nitrogen atmosphere, 0.821 g of Licacid MH-700 was mixed with 9.179 g of Carbodilite V-02B to obtain a transparent resin composition. n = 3.0, and the content of each material does not satisfy all the relational expressions (1) to (3).

<Comparative Example 7>
Evaluation was performed using only Ricacid MH-700 as a resin composition.

<Comparative Example 8>
Carbodilite V-02B alone was evaluated as a resin composition.

<Comparative Example 9>
A 48% aluminum oxide octylate solution (manufactured by Hope Pharmaceutical Co., Ltd., Liquid Olype AOO), which is known as an organometallic water-capturing agent, was dried under a nitrogen atmosphere to obtain a transparent water-capturing agent.

Table 3 shows the contents of the carboxylic acid anhydride and the carbodiimide compound in the above Examples and Comparative Examples.

<Measurement of the amount of water captured>
About 1 g of the above resin composition is applied to one side of an aluminum plate (weight known) having a thickness of 0.1 mm and 50 mm × 50 mm, and by measuring the weight, the exact weight of the resin composition applied to the aluminum plate ( A) was determined. Next, it was sufficiently reacted with water in a constant temperature and humidity chamber at 40 ° C. and 90% Rh until the weight change disappeared. The reaction was confirmed by FT-IR, and the reaction was continued until the infrared absorption peaks (1785 cm ⁻¹ and 1862 cm ⁻¹ ) of the acid anhydride group of the resin composition disappeared. For reference, the infrared absorption peaks before and after the reaction of the resin composition of Example 11 are shown in FIG.
After confirming the reaction with water, the weight (B) increased before and after being left in a constant temperature and humidity chamber is obtained, and immediately dried by dry air until there is no weight change. The weight (C) of the water was determined. The amount of water captured (the amount of water captured by the reaction) was determined by the following equation.
Amount of captured water = ((B) − (C)) / (A) × 100 (% by weight)
The amount of water captured was evaluated according to the following criteria. The results are shown in Table 4.
(Evaluation criteria)
○: The amount of water captured is 1% by weight or more. ×: The amount of water captured is less than 1% by weight.

<Measurement of permeability>
The above resin composition was applied to one side of a commercially available slide glass for microscope observation having a thickness of 1 mm in a nitrogen atmosphere, and the film thickness was adjusted to 100 μm. The obtained sample was left to stand in a constant temperature and humidity chamber at 40 ° C. and 90% Rh for 2 days, and then left in a desiccator for 2 days to dry the adsorbed water, and then measurement was performed. In the analysis, a slide glass was used as the baseline. The minimum transmittance in the wavelength range of 400 nm to 800 nm was determined and evaluated according to the following criteria. The results are shown in Table 2.
(Evaluation criteria)
○: Minimum transmittance in the wavelength range of 400 nm to 800 nm is 90% or more ×: Minimum transmittance in the wavelength range of 400 nm to 800 nm is less than 90%

<Measurement of flexibility>
The above resin composition was applied to one side of a commercially available PET film having a thickness of 100 μm in a nitrogen atmosphere, and the film thickness was adjusted to 100 μm. After leaving in a constant temperature and humidity chamber of 40 ° C. and 90% Rh for 2 days, the PET surface was bent along a cylindrical mandrel (R = 10 mm), and the state of the coating film was visually observed and evaluated according to the following criteria. . The results are shown in Table 4.
(Evaluation criteria)
○: No crack or dropout ×: Crack or dropout occurs

<Measurement of VOC>
The resin compositions of Example 11 and Comparative Example 9 were applied to a 100 μm aluminum plate so as to have a film thickness of 100 μm, and dried at 120 ° C. for 1 hour in a nitrogen atmosphere. VOC measurement was performed at 120 ° C. for 15 minutes with a purge and trap-GC / MS, and evaluation was performed according to the following criteria. The results are shown in Table 5.

(VOC evaluation criteria)
○: Total VOC is less than 2,000 ppm Δ: Total VOC is 2,000 ppm or more and less than 10,000 ppm x: 10,000 ppm or more

In Examples 10 to 14, the amount of captured water, light transmittance, flexibility, and VOC were good. On the other hand, in Comparative Example 5 where n = 0.1 and Comparative Example 7 using only the carboxylic acid anhydride, the dicarboxylic acid produced by the reaction with water crystallized, and the permeability was significantly reduced. In addition, it was found that Comparative Example 6 in which n = 3.0 and Comparative Example 8 in which only the carbodiimide compound was used did not express a sufficient amount of water. Further, the aluminum oxide octylate of Comparative Example 9 was poor in flexibility, cracks were generated, and VOC was high. From the above, in the present invention, it is possible to obtain a good water catching agent with less VOC than the conventional organometallic water catching agent. It can also be seen that the combined use of the carboxylic acid anhydride and the carbodiimide compound and satisfying all the relational expressions (1) to (3) can achieve both the amount of water trapping, permeability and flexibility.

[Resin Composition of Embodiment 1]
<Example 16> (system in which a catalyst is added and a thiol compound is added)
Under nitrogen atmosphere, 4 g of MHAC-P (Hitachi Chemical Co., Ltd. trade name, methyl-3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride, acid anhydride equivalent 178 g / eq) Then, 0.2 g of 1,8-diazabicyclo (5,4,0) undec-7-ene was added as a catalyst and stirred uniformly. Next, 2.7 g of NK Oligo UA-122P (trade name, Shin-Nakamura Chemical Co., Ltd., molecular weight 1,100, 43,000 mPa · s / 40 ° C.) as urethane acrylate, and 0.2 g of triglyceride as acrylate monomer Methylolpropane triacrylate, 0.3 g acryloylmorpholine, 0.1 g 1-hydroxy-cyclohexyl-phenyl-ketone as photopolymerization initiator, 2.5 g pentaerythritol tetrakis (3-mercaptopropionate as thiol compound) ) Was added and stirred uniformly. The resin composition was laminated between release PET films, and UV irradiation was performed to form the resin composition into a 100 μm sheet.
By UV irradiation, it was confirmed by FT-IR and GPC that a part of the thiol compound reacted with the double bond of MHAC-P.
Here, the content of the carboxylic anhydride group in the resin composition is 2.22 mmol / g.

<Example 17> (A system in which a thiol compound is added without adding a catalyst)
A resin composition was prepared in the same manner as in Example 15 except that 1,8-diazabicyclo (5,4,0) undec-7-ene was not added, and molded into a 100 μm sheet.
Here, the content of the carboxylic anhydride group in the resin composition is 2.22 mmol / g.

<Example 18> (System in which neither catalyst nor thiol compound is added)
Example 15 except that 1,8-diazabicyclo (5,4,0) undec-7-ene was not added and the total amount of pentaerythritol tetrakis (3-mercaptopropionate) was replaced with NK oligo UA-122P. A resin composition was prepared in the same manner as described above and molded into a 100 μm sheet.
Here, the content of the carboxylic anhydride group in the resin composition is 2.22 mmol / g.

(Improvement of water collection performance by adding catalyst)
Differences in water catching performance were compared between Example 16 and Example 17, which differed only in the presence or absence of the catalyst 1,8-diazabicyclo (5,4,0) undec-7-ene.
The sheets of Examples 16 and 17 were cut into 5 cm squares, sealed in a 50 ml sealed container equipped with a high-glosson temperature / humidity logger (KN Laboratories, Inc., compact temperature / humidity logger), and the humidity change inside the container was recorded. did.

Both were 46% Rh immediately after encapsulation, but the relative humidity after 5 hours was about 4% Rh in Example 16, but about 20% Rh in Example 17.

In Examples 16 and 17, a decrease in relative humidity was observed, but in Example 16 where the catalyst was added, the decrease in humidity was clearly faster, and the catalyst promoted the reaction between the carboxylic acid anhydride and water. It is suggested that

(Reduction in heat loss by adding thiol compound)
The weight loss by heating was compared between Example 17 to which pentaerythritol tetrakis (3-mercaptopropionate), which is a thiol compound, was added, and Example 18 to which no thiol compound was added. Each sheet was cut into 4 mm squares and examined for weight loss after heating in a nitrogen atmosphere at 120 ° C. for 4 hours using a TGA (thermogravimetric apparatus). Example 17 with the addition of the thiol compound had a weight loss of less than 5%, while Example 18 without the addition of the thiol compound had a weight loss of 5% or more. Although both are at a practical level, it has been found that the addition of a thiol compound can reduce the heat loss.

The mercapto group is considered to be able to react with any of a double bond of acryloyl group, a double bond of norbornene skeleton of MHAC-P, and an acid anhydride group. However, the resin composition of Example 17 was subjected to UV irradiation before and after UV irradiation. It was confirmed by FT-IR and NMR that both the mercapto group and the double bond of MHAC-P were decreased, and the amount of the low molecular weight component in the resin composition was also decreased as compared with Example 18. Was confirmed by GPC.
That is, it was found that a considerable mercapto group reacted with the double bond of the norbornene skeleton of MHAC-P.

1 Substrate 2 Sealing cap (plastic film)
3 Electrode 4 Organic functional layer 5 Electrode 6 Drying means 7 Sealing adhesive

Claims

A resin composition comprising at least one carboxylic acid anhydride and a non-reactive resin having no reactivity with a carboxylic acid anhydride group, the content of the carboxylic acid anhydride group in the resin composition Is 0.556 mmol / g or more, and the total light transmittance when the resin composition is molded to a thickness of 100 μm is 80% or more.
The resin composition according to claim 1, wherein the carboxylic acid anhydride is an alicyclic carboxylic acid anhydride.
At least one carboxylic acid anhydride and one carbodiimide compound are contained, and the contents of all carboxylic acid anhydrides and all carbodiimide compounds satisfy the following relational expressions (1) to (3): 40 ° C., 90% The resin composition according to claim 1 or 2, wherein the amount of water captured under the Rh condition is 1% by weight or more.
(1) A ≧ α / 18
(2) B = Anβ / α (provided that 0.25 ≦ n ≦ 2.5)
(3) A + B ≦ 100
(here,
A: Content (% by weight) of total carboxylic acid anhydride in the resin composition
B: Content (% by weight) of all carbodiimide compounds in the resin composition
α: acid anhydride equivalent of all carboxylic acid anhydrides (g / eq)
β: carbodiimide equivalent of all carbodiimide compounds (g / eq)
Indicates. )
A water-absorbing agent using the resin composition according to any one of claims 1 to 3.
The water-absorbing agent according to claim 4, comprising a mixture of carboxylic acid anhydrides composed of two or more kinds of carboxylic acid anhydrides.
Any non-reactive resin selected from poly (meth) acrylate, urethane (meth) acrylate and its cured product, polyester, polyvinyl ester, polyolefin, polystyrene, epoxy resin cured product, polycarbodiimide and copolymers thereof The water-absorbing agent according to claim 4 or 5, which is one or more kinds.
A laminated film having a layer containing the water-absorbing agent according to any one of claims 4 to 6.
An organic electronic device having a layer containing the water capturing agent according to any one of claims 4 to 6.
An organic EL device using the water-absorbing agent according to any one of claims 4 to 6.
An organic electronic device using the laminated film according to claim 7.
An organic EL device using the laminated film according to claim 7.