JPWO2011027658A1 - Composition, cured body and electronic device, and tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum and method for producing the same - Google Patents

Abstract

The composition concerning this invention contains the compound (A) shown by following General formula (1), and the polymeric compound (B) which has a cyclic ether structure at least, Content of the said compound (A) ( The content ratio (WA / WB) of WA) and the content (WB) of the compound (B) is 0.2 or more and 5 or less. (R1-O) nM (1) (In the above formula (1), R1 is an organic group. N is 2 or 3, and is equal to the valence of M. Plural R1s are the same or different. M is a divalent or trivalent atom.)

Description

  The present invention relates to a composition, a cured body formed from the composition, and an electronic device including the cured body. Furthermore, the present invention relates to a novel tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum and a method for producing the same.

  Electronic devices that are damaged by moisture, such as capacitors and organic EL elements, need to be used in a sealed state in order to eliminate moisture. However, only the sealant used in such a sealed electronic device cannot completely prevent moisture from entering. For this reason, unless there is a mechanism for removing moisture that gradually enters the device, the function of the electronic device gradually deteriorates with time.

  For example, an organic EL element that is a typical sealed electronic device has a problem in that light emission characteristics such as luminance and light emission efficiency are gradually lowered due to moisture that has entered the organic EL element as the driving period becomes longer. is there.

  As a means for protecting such a sealed electronic device from moisture entering from the outside, for example, in JP-A-2005-298598 and JP-T-2008-518399, a moisture scavenger is disposed in the device in advance, A technology for maintaining a low humidity environment is being studied.

  However, such a moisture scavenger produces a decomposition product by reacting with water. In particular, when the moisture scavenger is an organometallic compound or a metal alkoxide, it reacts with water to produce decomposition products such as alkane and alcohol. When such decomposition products diffuse into the device, they may be absorbed by an organic material such as a charge transport layer or an organic light emitting layer constituting the device, or may cause a volume expansion of voids existing in the device. As a result, pinholes are generated in the device, and the device is deformed to promote moisture intrusion, thereby shortening the device life.

  Furthermore, generally, it is necessary to form a coating liquid by dissolving a moisture scavenger in a solvent, forming the coating liquid by a coating method such as spin coating, and removing the solvent. However, when molded by such a method, the solvent may remain in the film, which may cause the same problem as described above. Therefore, it has been desired to develop a moisture scavenger from which the solvent is removed as much as possible.

  In addition, such a moisture scavenger may be deformed by heat flow under use environment (for example, about 80 ° C.) or may become opaque by reacting with water.

  On the other hand, since the moisture scavenger is usually formed on the surface of a glass substrate or the like, it is required to have excellent film formability and excellent glass adhesion.

  Therefore, some embodiments according to the present invention solve the above-mentioned problems, and are excellent in water absorption, heat fluidity (heat resistance), and also excellent in transparency, film formability, and glass adhesion. The present invention provides a moisture capturing composition capable of forming a body, a cured body formed from the composition, and an electronic device provided with the cured body.

  Furthermore, some embodiments according to the present invention provide tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum having an excellent moisture trapping action for solving the above-described problems, and a method for producing the same. It is to provide.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the composition according to the present invention is:
Compound (A) represented by the following general formula (1),
A polymerizable compound (B) having at least a cyclic ether structure;
Containing
The content of the compound _{(A) (W} A) and the compound content of _{(B) (W} B) and the content ratio _(W A / W _B) is a feature that is 0.2 to 5 To do.
(R ¹ -O) nM (1)
(In the above formula (1), R ¹ is an organic group. N is 2 or 3, and is equal to the valence of M. A plurality of R ¹ may be the same or different. M is divalent or (It is a trivalent atom.)

[Application Example 2]
In application example 1,
The boiling point of the alcohol (R ¹ —OH) produced by hydrolysis of the compound (A) represented by the general formula (1) can be 200 ° C. or higher under 1 atm.

[Application Example 3]
In application example 1 or application example 2,
The M in the general formula (1) may be aluminum.

[Application Example 4]
In any one of Application Examples 1 to 3,
The compound (A) may be a compound represented by the following formula (2).

[Application Example 5]
In any one of Application Examples 1 to 4,
The cyclic ether structure of the polymerizable compound (B) may be an epoxy group or an oxetanyl group.

[Application Example 6]
The composition described in any one of the application examples 1 to 5 can be used for the purpose of capturing moisture.

[Application Example 7]
One aspect of the cured body according to the present invention is:
It was formed using the moisture capturing composition described in Application Example 6.

[Application Example 8]
One aspect of the electronic device according to the present invention is:
The cured product according to Application Example 7 is provided.

[Application Example 9]
Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum according to the present invention is a compound represented by the following formula (2).

[Application Example 10]
One aspect of the method for producing the compound represented by the above formula (2) according to the present invention is as follows:
It is produced by reacting trimethylolpropane diallyl ether with triisobutylaluminum.

  The composition according to the present invention is excellent in hygroscopicity and heat resistance, and can form a cured body (coating film, film, etc.) that is also excellent in transparency, film formability, and glass adhesion. The cured body is not deformed by heat flow even under a use environment exceeding 80 ° C., for example.

  Furthermore, the composition concerning this invention can take the aspect which does not contain a solvent. According to this aspect, the solvent does not remain in the cured body. Therefore, by mounting the cured body in the electronic device, it is possible to prevent harmful effects that occur in the electronic device due to the solvent remaining in the cured body, for example, the occurrence of pinholes and moisture intrusion due to device deformation. .

  The cured body is suitable for use as a moisture scavenger in an electronic device such as an organic EL element, and when it is excellent in transparency, it can be used, for example, in a top emission type organic EL element.

FIG. 1 is a cross-sectional view schematically showing an example of the organic EL element according to the first embodiment. FIG. 2 is a cross-sectional view schematically showing an example of the organic EL element according to the second embodiment. FIG. 3 is a ¹ H-NMR spectrum of tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, Various modifications implemented in the range which does not change the summary of this invention are also included.

1. Composition The composition concerning this Embodiment is
A compound (A) represented by the following general formula (1) (hereinafter also simply referred to as “component (A)”) and a polymerizable compound (B) having at least a cyclic ether structure (hereinafter simply referred to as “component (B)”) "), And
The content of the component (A) _{(W A)} and (B) the content of the component _{(W B)} and the content ratio _(W A / W _B), and wherein a is 0.2 to 5 To do.
(R ¹ -O) nM (1)
(In the above formula (1), R ¹ is an organic group. N is 2 or 3, and is equal to the valence of M. A plurality of R ¹ may be the same or different. M is divalent or (It is a trivalent atom.)

  Hereinafter, each component which comprises the composition concerning this Embodiment is demonstrated.

1.1. (A) component The composition concerning this Embodiment contains the compound (A) shown by following General formula (1).
(R ¹ -O) nM (1)
(In the above formula (1), R ¹ is an organic group. N is 2 or 3, and is equal to the valence of M. A plurality of R ¹ may be the same or different. M is divalent or (It is a trivalent atom.)

  The component (A) is a component obtained by reacting an OM bond (where O represents an oxygen atom and M represents a divalent or trivalent atom) present in the component (A) with moisture. Can be captured. By using such a component (A), a cured product having excellent hygroscopicity can be obtained.

In the general formula (1), R ¹ is an organic group, specifically, the same or different substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cyclic alkyl group, or aryl group. . These organic groups may be linear or have a branched chain. When R ¹ is an alkenyl group or an alkynyl group, the position and number of double bonds and triple bonds are not particularly limited.

The number of carbon atoms of ^{R 1} is preferably 6 to 30, more preferably from 10 to 20, particularly preferably from 12 to 20. It is preferable that the carbon number of R ¹ is 6 to 30 because, when the component derived from R ¹ is liberated by hydrolysis, it is difficult to become a component of outgas and easily forms a uniform mixture with the component (B) described later. .

  Examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, tetramethylhexadecyl group, octadecyl group and the like.

  Examples of the alkenyl group include octenyl group, dodecenyl group, octadecenyl group, allyl group and the like.

  Examples of the alkynyl group include a phenylethynyl group.

  Examples of the cyclic alkyl group include a cyclohexyl group.

  Examples of the aryl group include a phenyl group and a benzyl group.

Hydrolysis of the compound represented by the general formula (1) generates alcohol (R ¹ —OH) as a decomposition product. The boiling point of R ¹ —OH is preferably 200 ° C. or higher, more preferably 250 ° C. or higher at 1 atmosphere. If it is 200 degreeC or more, the spreading | diffusion in the electronic device of R < ¹ > -OH can be suppressed.

  In the general formula (1), M is a divalent or trivalent atom. Examples of such atoms include Group 2 elements, Group 4 elements, Group 12 elements, and Group 13 elements in the IUPAC periodic table, such as Al, B, Mg, Zn, Ti, and Zr. Can be mentioned. Among these, Al is preferable from the viewpoint of being excellent in hygroscopicity and capable of maintaining transparency after being decomposed by trapping moisture without being colored.

  Specific examples of the compound represented by the general formula (1) include, for example, trihexyloxyaluminum, trioctyloxyaluminum, tridecyloxyaluminum, tridodecyloxyaluminum, trioctadecyloxyaluminum, tri (2,2-bis (Allyloxymethyl) -1-butoxy) aluminum, tridecyloxyborane, tridodecyloxyborane, trioctadecyloxyborane and the like.

Among the compounds represented by the above general formula (1), a compound in which R ¹ is an organic group having 12 or more carbon atoms, such as tridodecyloxyaluminum, trioctadecyloxyaluminum, tri (2,2-bis (ary Roxymethyl) -1-butoxy) aluminum is preferred, and tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum is more preferred. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum is a novel compound having an excellent moisture trapping action and has a structure represented by the following formula (2). Detailed description will be described later.

  The content of the component (A) in the composition according to the present embodiment is preferably 10% by mass to 90% by mass, and more preferably 50% by mass when the total mass of the composition is 100% by mass. % To 80% by mass. It is preferable for the content of component (A) to be in the above range since the action of capturing moisture can be effectively expressed in the cured body. Furthermore, when the content of the component (A) is in the above range, an appropriate viscosity as described later can be imparted to the composition, and workability such as film formability when forming a cured product is good. Become.

1.2. (B) Component The composition concerning this Embodiment contains the polymeric compound (B) which has a cyclic ether structure at least. The cyclic ether structure is preferably an epoxy group or an oxetanyl group, and more preferably an epoxy group.

  Examples of the component (B) include bisepoxycyclohexanecarboxylate, diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, xylylenebisoxetane, 3-ethyl-3 {[((3-ethyloxetane-3- Yl) methoxy] methyl} oxetane and the like, but is not limited thereto. Among these, bisepoxycyclohexanecarboxylate and diepoxylimonene having an epoxy group are preferable, and bisepoxycyclohexanecarboxylate is more preferable. This is because bisepoxycyclohexanecarboxylate can be cured by heat even in the absence of a curing agent such as an acid generator.

  In the cured product obtained by curing the composition according to the present embodiment, the cyclic ether structure in component (B) reacts to form a polymer compound having a repeating unit derived from component (B). Is done. Such a polymer compound may have a structure in which repeating units derived from the component (B) are bonded to each other, or the repeating unit derived from the component (B) and the repeating unit derived from the component (A) described above are shared. It may be a polymerized structure.

  Hereinafter, the functions of the component (B) will be listed and described.

  1stly, (B) component can hold | maintain decomposition products, such as alcohol and alkane produced | generated when (A) component reacts with a water | moisture content. The component (A) is fixed in the polymer compound when the polymer compound derived from the component (B) is formed. As a result, the decomposition product generated when the component (A) reacts with moisture is efficiently absorbed in the polymer compound derived from the component (B), so that the decomposition product diffuses into the electronic device. Can be suppressed.

  Secondly, the composition can be made solvent-free by using the component (B). Since the component (B) can be arbitrarily mixed with the component (A), a solvent for dissolving the component (A) becomes unnecessary. Thereby, the bad effect by a solvent remaining in the hardening body as mentioned above can be prevented.

  Thirdly, the component (B) can suppress the thermal fluidity of the cured body. As described above, the component (B) undergoes a polymerization reaction when the composition according to the present embodiment is cured to produce a polymer compound. This polymer compound can suppress the heat fluidity of the cured body while maintaining the hygroscopic ability of the component (A) described above.

  4thly, moderate viscosity can be provided to a composition by adding (B) component. Thereby, the film-forming property of the composition concerning this Embodiment can be improved.

  Fifth, since the component (B) can be arbitrarily mixed with the component (A), the transparency of the cured product obtained by curing the composition can be improved.

  The content of the component (B) in the composition according to the present embodiment is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass when the total mass of the composition is 100% by mass. % Or more and 50% by mass or less. When the content of the component (B) is in the above range, a good cured product can be formed without impairing each function described above.

1.3. Content ratio (W _A / W _B )
In the composition according to the present embodiment, the content ratio (W _A / W _B ) between the content (W _A ) of the component ( _A ) and the content (W _B ) of the component ( _B ) is 0. 2 or more and 5 or less. The content ratio (W _A / W _B ) is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less. When the content ratio (W _A / W _B ) is within the above range, the obtained cured body can ensure a sufficient water absorption capacity and have excellent heat resistance and glass adhesion. When the content ratio (W _A / W _B ) is less than 0.2, the water absorption capacity of the obtained cured product is reduced, and the function as a moisture scavenger is not sufficiently exhibited, and film forming properties and glass adhesion are pointed out. Tend to be inferior. On the other hand, when the content ratio (W _A / W _B ) exceeds 5, the water absorption capacity of the obtained cured product is sufficient, but it tends to be inferior in terms of heat resistance, film formability, and glass adhesion.

1.4. Other additives Various additives may be added to the composition according to the present embodiment as necessary. Examples of the various additives include known thermal acid generators or thermal base generators for imparting thermosetting properties, known photoacid generators or photobase generators for imparting photocurability, and known increasing agents. Examples include sensitizers. Examples of the thermal acid generator include aromatic sulfonium salts (manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sun-Aid SI-100L”) and the like.

  Moreover, you may add polymeric compounds other than the said (B) component to the composition concerning this Embodiment. Examples of the polymerizable compound other than the component (B) include (meth) acrylic acid, methyl methacrylate (MMA), ethyl methacrylate (EMA), propyl methacrylate (PMA), butyl methacrylate (BMA), and methacrylic acid. Ethylhexyl (EHMA), trimethoxysilylpropyl methacrylate (TMSPMA), tertiary butyl methacrylate (t-BMA), hydrogenated methacrylic acid butadiene (trade name “L1253” manufactured by Kuraray Co., Ltd.), methyl acrylate, acrylic acid Examples thereof include polymerizable compounds having an acrylic group such as ethyl and benzyl acrylate; polymerizable compounds having a vinyl ether group such as triethylene glycol divinyl ether; and polymerizable compounds having a vinyl group such as vinylcyclohexene monooxide. These polymerizable compounds may be used singly or in combination of two or more.

  Moreover, you may mix a heat conductive filler with the composition concerning this Embodiment in order to improve heat conductivity as needed. In the organic EL lighting device in which a plurality of organic EL elements are used, in which the composition according to the present embodiment is used, the temperature in the vicinity of the elements may increase due to heat generation. As a result, there may be a disadvantage that the light emission characteristics such as luminance and light emission efficiency are adversely affected. However, it is preferable to mix a heat-conducting filler because heat dissipation can be improved and the element can be protected from moisture, and at the same time, the element can be protected from adverse effects due to heat generation.

  Known fillers such as inorganic particles can be used as the heat conductive filler. When inorganic particles are used as the heat conductive filler, not only the thermal conductivity of the cured product formed using the composition according to the present embodiment is improved, but the component (A) is decomposed by moisture absorption. The component (decomposition product) generated in this manner is adsorbed to suppress diffusion to the binder component (matrix), and the decomposition product can be captured inside the cured body. Thereby, it can prevent that the said decomposition product acts as a plasticizer of a hardening body. That is, the cured body formed using the composition according to the present embodiment is not deformed by heat flow even in a use environment exceeding 80 ° C., for example. Furthermore, other functions of the inorganic particles include improving the mechanical strength of a cured product formed using the composition according to the present embodiment, increasing the hygroscopic capacity of the cured product, and the like.

  In the present invention, “inorganic particles” refer to particles formed from compounds other than organic compounds having carbon atoms in the basic skeleton of the structure, and also include particles formed from allotropes of carbon.

  The material of the inorganic particles is preferably a metal oxide or a metal nitride. Examples of the metal oxide include silica (including silica gel), smectite, zeolite, alumina, titanium oxide, zirconia, magnesia, and various glass powders used for heat dissipation materials. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride. Moreover, although it is not a metal oxide or a metal nitride, silicon carbide, boron carbide, and activated carbon can also be used as inorganic particles. Among these, from the viewpoint of suppressing thermal fluidity, it is preferably at least one particle selected from alumina, silica, boron nitride, aluminum nitride, silicon nitride, magnesia, silicon carbide, boron carbide and smectite, Further, from the viewpoint of excellent thermal conductivity, alumina and / or boron nitride particles are particularly preferable. These inorganic particles may be used alone or in combination of two or more.

  The method for producing the silica particles used in the present embodiment is not particularly limited, and a conventionally known method can be applied. For example, it can be produced according to the method for producing a silica particle dispersion described in JP-A No. 2003-109921 and JP-A No. 2006-80406. Further, as a conventionally known method, there is a method of producing silica particles by removing alkali from an alkali silicate aqueous solution. Examples of the alkali silicate aqueous solution include a sodium silicate aqueous solution, an ammonium silicate aqueous solution, a lithium silicate aqueous solution, and a potassium silicate aqueous solution that are generally known as water glass. Examples of ammonium silicate include silicates made of ammonium hydroxide and tetramethylammonium hydroxide.

  The silica particles used in the present embodiment are preferably hydrophobically modified. “Hydrophobic modification” means that a hydrogen atom of a silanol group (—SiOH) present in silica particles is substituted with a hydrophobic group (—R) such as an alkyl group. Silanol groups present on the surface of the silica particles tend to reduce the water absorption capacity of the cured product formed from the composition according to the present embodiment by reacting with the component (A). Therefore, it is possible to suppress a decrease in water absorption ability of the cured body by hydrophobically modifying the silanol group present on the surface of the silica particles. Moreover, the dispersibility of the silica particle at the time of mixing improves by performing the hydrophobic modification of the silica particle.

  The shape of the inorganic particles is not particularly limited, and may be spherical or elliptical, or may be a polygonal shape. The inorganic particles may be porous particles, or core / shell particles having a hollow inside.

  The average particle diameter of the inorganic particles is preferably 5 to 5,000 nm, more preferably 5 to 2,000 nm, still more preferably 5 to 500 nm, and particularly preferably 5 to 100 nm. When the average particle diameter is within the above range, deformation due to heat flow of the cured body formed using the composition according to the present embodiment can be prevented. Particularly when the average particle size is 5 to 100 nm, it is advantageous in that a cured product having excellent transparency can be formed. When the average particle size is within the above range, it becomes easy to impart an appropriate viscosity as described later to the composition, and workability (applicability, etc.) when forming a cured product is improved. Furthermore, when the average particle diameter is within the above range, the inorganic particles have a surface area sufficient to capture the decomposition products, thereby suppressing deformation due to heat flow of the cured body. preferable.

  In addition, although it is preferable that the average particle diameter of an inorganic particle is computed from the specific surface area measured using BET method, it is not limited to this, It can also measure by another well-known method.

  The average particle size of the inorganic particles is measured by collecting the cured body formed from the composition according to the present embodiment, cutting the cured body, and observing the cut surface with an electron microscope or the like. You can also. By measuring by this method, the average particle diameter of the inorganic particles can be measured even after the cured body is formed.

  The content of the inorganic particles in the composition according to the present embodiment is preferably 0.1% by mass or more from the viewpoint of improving the thermal conductivity of the cured body when the total mass of the composition is 100% by mass. It is 80 mass% or less, More preferably, it is 20 mass% or more and 60 mass% or less. Furthermore, from the viewpoint of ensuring the transparency of the cured body, it is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less. In addition, if content of an inorganic particle is 0.1 mass% or more, the hardening body which does not deform | transform by heat flow can be obtained.

1.5. Manufacturing method of composition The composition concerning this Embodiment can be manufactured by mixing the (A) component mentioned above, the (B) component, and the other additive mentioned above as needed. The method of mixing these components is not particularly limited, but the composition according to the present embodiment can be easily obtained by adding and dissolving the component (A) little by little while stirring the component (B). it can.

1.6. Physical Properties and Use of Composition The composition according to the present embodiment preferably has a viscosity of 50 to 500,000 cP. When the viscosity is in the above range, the composition can be directly applied to the element substrate by the ODF method and cured. This eliminates the need to prepare the composition according to the present embodiment in the form of a film or the like in advance and incorporate it into the element, thereby simplifying the process. Further, if a photoacid generator or the like is added to the composition according to the present embodiment to impart photosensitivity, fine patterning becomes possible. In addition, the said viscosity shows the value measured by the falling needle method.

  Since the composition concerning this Embodiment can form the hardening body containing (A) component, it can be used for the use which capture | acquires a water | moisture content. The composition according to the present embodiment can be used as a moisture scavenger for organic EL elements, organic TFTs, organic solar cells, organic CMOS sensors and the like, and is particularly suitably used as a moisture scavenger for organic EL elements.

2. Cured body In the present invention, the “cured body” means a film whose viscosity or hardness has increased from that of the original composition by forming or molding the above composition into a shape suitable for use and further heating or irradiating with light. Say.

  The cured body according to the present embodiment can be obtained, for example, by applying the above composition onto a substrate such as a glass substrate to form a film, and then curing it by heating or light irradiation.

  Examples of the coating method include a spin coater, a roll coater, a spray coater, a dispenser, and a method using an ink jet apparatus.

  Although the temperature in the case of hardening is not specifically limited, For example, it is 50 to 150 degreeC.

  Although the shape of the obtained hardening body is not specifically limited, For example, it has a film shape. When this hardening body has a film shape, the film thickness is 5-100 micrometers, for example.

  The content of the component (A) in the cured product according to the present embodiment is preferably 10% by mass or more and 90% by mass or less, more preferably 50% by mass or more when the total mass of the cured product is 100% by mass. 80% by mass or less. It is preferable for the content of the component (A) to be in the above range since the function of capturing moisture can be sufficiently expressed. Furthermore, it is preferable that the content of the component (A) is in the above-mentioned range because the film formability is improved and the cured body is easily imparted with transparency.

3. Electronic Device The electronic device according to the present embodiment includes the cured body inside the electronic device. The cured body can be mounted on any electronic device as long as it is an electronic device that dislikes moisture. Hereinafter, an example of an organic EL element, which is a typical sealed electronic device, will be described with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing an organic EL element 100 according to the first embodiment. As shown in FIG. 1, the organic EL element 100 includes an organic EL layer 10, a structure 20 that houses the organic EL layer and blocks it from the outside air, and a trapping agent layer 30 formed in the structure 20. Is composed of.

  The organic EL layer 10 may have a structure in which an organic light emitting material layer made of an organic material is sandwiched between a pair of electrodes facing each other, for example, anode / charge (hole) transport agent / light emitting layer / cathode. A known structure such as the above can be adopted.

  The scavenger layer 30 is a cured product of the above composition. As shown in FIG. 1, the scavenger layer 30 is formed away from the organic EL layer 10.

  In FIG. 1, the structure 20 includes a substrate 22, a sealing cap 24, and an adhesive 26. Examples of the substrate 22 include a glass substrate, and examples of the sealing cap 24 include a structure made of glass. The structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated.

  FIG. 2 is a cross-sectional view schematically showing an organic EL element 200 according to the second embodiment. As shown in FIG. 2, the organic EL element 200 is different from the organic EL element 100 in that the capturing agent layer 30 formed in the structure 20 is formed in close contact with the organic EL layer 10. Since the scavenger layer 30 is a cured body with little residual or generated volatile components, the display characteristics of the organic EL layer 10 are not impaired. In addition, the trapping agent layer 30 can protect the organic EL layer 10 while preventing moisture from entering the organic EL layer 10.

4). Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum The present inventors have found that the compound represented by the following formula (2) has an excellent moisture capturing function. That is, the compound represented by the following formula (2) can be used as one of the components (A) constituting the above-described composition.

  The compound represented by the following formula (2) has a feature that the boiling point of the alcohol produced by reacting with moisture is 258 ° C. under 1 atm, and produces an alcohol that is not easily volatilized under the use environment. Yes. Furthermore, the compound represented by the following formula (2) is excellent in compatibility with the above-mentioned compound (B), and a transparent composition can be produced.

  Hereinafter, the manufacturing method of the compound shown by the said Formula (2) is demonstrated. The compound represented by the above formula (2) of the present invention is obtained by adding triisobutylaluminum little by little to 3 to 3.5 equivalents of trimethylolpropane diallyl ether while stirring, and at an appropriate temperature of 0 to 150 ° C. for 1 hour. Can be easily produced by reacting for 4 hours. Then, the compound shown by said Formula (2) is obtained by post-processing in accordance with a conventional method.

  By the above method, the compound represented by the above formula (2) can be obtained as an oily substance, and if necessary, it can be made into a purified product with higher purity by performing column chromatography if necessary.

5. Example 5.1. Synthesis of tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum In a 500 mL three-necked flask, 162.0 g of trimethylolpropane diallyl ether (trade name “Neoallyl T-20” manufactured by Daiso Corporation) [ 756 mmol] was added, and 50.0 g [252.7 mmol] of triisobutylaluminum was added dropwise in a glow box while stirring. After stirring for 1 hour, the mixture was stirred at 120 ° C. for 90 minutes. While maintaining the temperature at 120 ° C., the unreacted raw material was distilled off while reducing the pressure with a vacuum pump, cooled to room temperature, and tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum (hereinafter, “ 164.0 g) (referred to as “TMDE-3”) was obtained as a colorless transparent oil. The yield was quantitative.

FIG. 3 is a ¹ H-NMR spectrum of the resulting tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum. ^{In 1} H-NMR measurement, toluene-d8 (near peak δ2.1) was used as an internal standard substance. FIG. 3 shows that the obtained compound has a chemical structure represented by the above formula (2).

Further, tri (2,2-bis () was prepared in the same manner as in the above method except that the amount charged was changed to 162.0 g [756 mmol] trimethylolpropane diallyl ether and 60.0 g [303.2 mmol] triisobutylaluminum. 172.0 g of a mixture containing allyloxymethyl) -1-butoxy) aluminum (hereinafter referred to as “TMDE-3B”) was obtained. As a result of ¹ H-NMR measurement of the obtained TMDE-3B in the same manner as TMDE-3, it was found to be a mixture containing a compound having a chemical structure represented by the above formula (2).

Further, tri (2,2-bis () was prepared in the same manner as in the above method except that the charged amount was changed to 194.4 g [907 mmol] of trimethylolpropane diallyl ether and 50.0 g [252.7 mmol] of triisobutylaluminum. 194.0 g of a mixture containing allyloxymethyl) -1-butoxy) aluminum (hereinafter referred to as “TMDE-3C”) was obtained. As a result of ¹ H-NMR measurement of the obtained TMDE-3C in the same manner as TMDE-3, it was found to be a mixture containing a compound having a chemical structure represented by the above formula (2).

  The mixture (TMDE-3B, TMDE-3C) containing tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum (TMDE-3) and TMDE-3 thus obtained is described below. In Examples and Comparative Examples shown, it was used as the component (A).

5.2. (B) Component As the (B) component, the following commercially available compounds were used.
・ Bisepoxycyclohexanecarboxylate (Daicel Chemical Industries, trade name “Celoxide 2021”)
・ 1,2: 8,9-diepoxy limonene (manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 3000”)
・ Xylylenebisoxetane (trade name “Aron Oxetane OXT-121”, manufactured by Toa Gosei Co., Ltd.)
3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name “Aronoxetane OXT-221” manufactured by Toa Gosei Co., Ltd.)
・ Bisepoxy oligoethylene glycol (trade name “Denacol EX-830” manufactured by Nagase ChemteX Corporation)

5.3. Examples and Comparative Examples 5.3.1. Production of Film Films to be evaluated in Examples 1 to 9 and Comparative Examples 1 to 5 were produced as follows.

  First, in a glove box having a dew point of −60 ° C. or less and an oxygen of 5 ppm or less, the component (A), the component (B), and other additives as necessary are combined with the compositions described in Table 1 or Table 2. By sufficiently stirring and mixing, compositions A to N were obtained.

  Subsequently, the obtained composition was apply | coated on the glass substrate, it was thermoset by heating at 80 degreeC for 1 hour, and the film was shape | molded. It shows in Table 1 and Table 2 about the composition of composition A-N.

In addition, the abbreviation of the component in Table 1 or Table 2 represents the following component, respectively.
“TMDE-3”; tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum “CE-2021”; bisepoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name “Celoxide 2021” ")
"CE-3000"; 1,2: 8,9-diepoxy limonene (manufactured by Daicel Chemical Industries, Ltd., trade name "Celoxide 3000")
"OXT-121"; xylylene bisoxetane (manufactured by Toa Gosei Co., Ltd., trade name "Aron Oxetane OXT-121")
"OXT-221"; 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (product name "Aronoxetane OXT-221" manufactured by Toagosei Co., Ltd.)
・ "EX-830"; bisepoxy oligoethylene glycol (manufactured by Nagase ChemteX Corporation, trade name "Denacol EX-830")
・ "TMPT"; Trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "NK Ester TMPT")
-"SI-100L": Aromatic sulfonium salt (manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sun-Aid SI-100L", thermal acid generator)

5.3.2. Evaluation method About each film obtained by said "5.3.1. Production of a film", hygroscopicity, transparency, film-forming property, and glass adhesiveness were evaluated by the following method. Further, the thermal fluidity was evaluated by separately producing a film by the following method. The results are also shown in Table 1 and Table 2.

(1) Hygroscopicity To a glass petri dish having an inner diameter of 3 cm, a film having a thickness of 0.6 mm is prepared for each film of Examples and Comparative Examples, and a vacuum desiccator with an internal volume of 800 cm ³ equipped with a hygrometer and a thermometer. The previously produced film was put together with the glass petri dish, and the changes in humidity and temperature inside the vacuum desiccator were measured. From the relative humidity (Hr,%) and the temperature in degrees Celsius (Tc, ° C) obtained by the measurement, the absolute humidity (Ha,%) was obtained by the following formula (3). And the reduction rate of absolute humidity Ha (2h) 2 hours after absolute humidity Ha (0h) at the time of a measurement start was made into water absorption, and the water absorption was computed and evaluated by following formula (4).
Ha = 4.0 × 10 ⁻³ {exp (6.4 × 10 ⁻² · Tc)} Hr (3)
Water absorption rate (%) = 100 × (Ha (0h) −Ha (2h)) / Ha (0h) (4)
The water absorption rate (%) is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more.

(2) Thermal fluidity (heat resistance)
First, an appropriate amount of any one of Compositions A to N was put in a sample tube, and heated at 80 ° C. for 60 minutes to produce a film having a thickness of 2 mm on the bottom of the sample tube. Next, after sufficiently absorbing the film in the atmosphere, the lid is further closed and sealed, and the sample tube is placed in an environment of 85 ° C. with the bottom of the sample tube being fixed (the film formation surface is upward). Left to stand. Thereafter, the state of the film when 336 hours passed was observed. The evaluation criteria for heat fluidity were “◯” when no change was observed in the film, and “X” when the film was slid downward and deformation was observed.

(3) Transparency Regarding the film obtained in the above “5.3.1. Production of film”, “O” indicates that no cloudiness is observed by visual observation, and “X” indicates cloudiness. In addition, when applying to uses, such as top emission type organic EL etc. in which transparency is requested | required, a thing with favorable transparency is preferable.

(4) Film-forming property About the film obtained by said "5.3.1. Production of film", the film which is not visually cracked and uneven | corrugated is "(circle)", and a crack or unevenness | corrugation is recognized by the film. The case where it was answered was set as “x”. In addition, when applying to uses, such as organic EL, what suppressed generation | occurrence | production of a crack and an unevenness | corrugation is preferable.

(5) Glass Adhesiveness Regarding the film obtained in the above “5.3.1. Production of film”, the film that does not peel from the glass in the atmosphere is “◯”, and the film that peels is “x”. In addition, when applying to uses, such as a display material in which the adhesiveness to a glass substrate is requested | required, a thing with favorable glass adhesiveness is preferable.

5.3.3. Evaluation results From the results shown in Tables 1 and 2, according to the films formed from the compositions of Examples 1 to 9, all the compositions contained the component (A) and the component (B), and W _A / since the value of W _B is in the range of 0.2 to 5, it was found to have excellent moisture resistance and heat resistance. Moreover, according to the composition of Examples 1-9, it turned out that the film which is excellent also in transparency, film formability, and glass adhesiveness is obtained.

  On the other hand, Comparative Example 1 is an example in which calcium oxide generally used as a hygroscopic agent is used instead of the component (A). This calcium oxide was in a state of being dispersed without being dissolved in the component (B). In Comparative Example 1, since the solution was not cured and did not form a film, all the above evaluations could not be performed.

  Comparative Example 2 is an example in which calcium oxide generally used as a hygroscopic agent is used instead of the component (A), and a thermal acid generator is further used. This calcium oxide was in a state of being dispersed without being dissolved in the component (B). Thereby, as for the film formed from the composition of the comparative example 2, transparency and glass adhesiveness were impaired.

  Comparative Example 3 is an example in which TMPT is used instead of the component (B). In Comparative Example 3, as in Comparative Example 1, the solution was not cured and did not form a film, and thus all the above evaluations could not be performed.

Comparative Example _4, the value of W A / _{W B} are examples of less than 0.2. The film formed from the composition of Comparative Example 4 had a low water absorption rate, and film formability and glass adhesion were also impaired.

Comparative Example 5 is an example in which the value of W _A / W _B exceeds 5. The film formed from the composition of Comparative Example 5 was impaired in heat resistance, as well as film formability and glass adhesion.

From the above results, containing components (A) and component (B), and the value of W A _/ W _B are formed from a composition in the range of 0.2 to 5 film, water absorption and It turned out that it was excellent in heat resistance, and it was excellent also in transparency, film-forming property, and glass adhesiveness.

DESCRIPTION OF SYMBOLS 10 ... Organic EL layer, 20 ... Structure, 22 ... Substrate, 24 ... Sealing cap, 26 ... Adhesive, 30 ... Capture agent layer, 100/200 ... Organic EL element

Claims (10)

Compound (A) represented by the following general formula (1),
A polymerizable compound (B) having at least a cyclic ether structure;
Containing
The content of the compound _{(A) (W} A) and the compound content of _{(B) (W} B) and the content ratio _(W A / W _B) is 0.2 to 5, the composition.
(R ¹ -O) nM (1)
(In the above formula (1), R ¹ is an organic group. N is 2 or 3, and is equal to the valence of M. A plurality of R ¹ may be the same or different. M is divalent or (It is a trivalent atom.) In claim 1,
The composition of the alcohol (R ¹ —OH) produced by hydrolysis of the compound (A) represented by the general formula (1) has a boiling point of 200 ° C. or more under 1 atmosphere. In claim 1 or claim 2,
The composition in which the M in the general formula (1) is aluminum. In any one of Claims 1 to 3,
The compound (A) is a composition represented by the following formula (2).

In any one of Claims 1 thru | or 4,
The cyclic ether structure of the compound (B) is an epoxy group or an oxetanyl group.   The moisture capturing composition according to any one of claims 1 to 5.   A cured body formed using the moisture capturing composition according to claim 6.   An electronic device comprising the cured body according to claim 7. Tri (2,2-bis (allyloxymethyl) -1-butoxy) aluminum represented by the following formula (2).

  The manufacturing method of the compound shown by Formula (2) of Claim 9 produced | generated by making triisobutylaluminum react with trimethylol propane diallyl ether.

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