KR20210116285A - Compound, photocurable composition, cured film, and organic electro luminescence element - Google Patents

Abstract

The present invention relates to a compound represented by chemical formula (1). In chemical formula (1), M represents titanium, zirconium or hafnium atom, and each of R^1, R^2, R^3 and R^4 represents an alkyl group that may be substituted with a polymerizable unsaturated bond-containing group, with the proviso that at least one of R^1, R^2, R^3 and R^4 represents an alkyl group substituted with a polymerizable unsaturated bond-containing group. When the compound is applied to a composition including polymerizable monomers, it is possible to remove water in the composition sufficiently and to maintain the storage stability of the composition sufficiently.

Description

A compound, a photocurable composition, a cured film, and organic electroluminescent element {COMPOUND, PHOTOCURABLE COMPOSITION, CURED FILM, AND ORGANIC ELECTRO LUMINESCENCE ELEMENT}

The present invention relates to a compound, a photocurable composition, a cured film, and an organic EL device.

As a sealing technique of the light emitting part of a top emission type organic electroluminescent element, the film|membrane sealing technique is known. The film sealing technique is a technique of forming and sealing an inorganic film and an organic film alternately with respect to the light emitting part. By the alternately laminated sealing film obtained in this way, penetration of moisture, etc. into a light emitting part can be prevented.

As a material which forms an organic film, the composition containing the combination of a polyethylene glycol di(meth)acrylate monomer and pentaerythritol tetra(meth)acrylate is disclosed, for example (refer patent document 1).

Patent Document 1: Japanese Patent Publication No. 2017-531049

However, since the polymerizable monomer which has a hydrophilic functional group contained in the composition described in patent document 1 tends to adsorb|suck moisture easily, the organic film formed may contain water|moisture content. When the moisture contained in the organic film penetrates into the light emitting portion, the light emitting area of the organic EL element becomes small, or dark spots may occur.

From a viewpoint of preventing such a phenomenon, it is considered to introduce|transduce a water catcher component into a composition. However, according to the study of the present inventor, when a typical aluminum alkoxide as a catcher component is applied to these compositions, due to the high reactivity (activity) of the aluminum alkoxide, some moisture causes alterations such as aggregation and cloudiness in the composition. In addition, the pot life time is short, and the curing reaction (polymerization reaction of the polymerizable monomer) of the composition proceeds during storage, increasing the viscosity, and there is a problem in storage stability, such as not being able to apply the composition. found out that there is a case.

Accordingly, the main object of the present invention is to provide a compound capable of sufficiently removing moisture in the composition and sufficiently maintaining storage stability of the composition when applied to a composition containing a polymerizable monomer.

One aspect of the present invention provides a compound represented by the following general formula (1).

In formula (1), M represents a titanium atom, a zirconium atom, or a hafnium atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group which may be substituted with a group containing a polymerizable unsaturated bond. However, ^{at least one (one or more) of R 1} , R ² , R ^{3 ,} and R ⁴ is an alkyl group substituted with a group containing a polymerizable unsaturated bond.

According to such a compound, when it applies to the composition containing a polymerizable monomer at the point which has water-retaining property equivalent to the typical aluminum alkoxide as a water-catching component, it is possible to fully remove the water|moisture content in a composition. Moreover, according to such a compound, since the activity in the polymerization reaction of a polymerizable monomer is moderate compared with the typical aluminum alkoxide as a catcher component, it can prevent that quality change will occur in a composition, and furthermore, of a polymerizable monomer Unintentional polymerization reaction can be suppressed. Therefore, when it applies to the composition containing a polymerizable monomer, it becomes possible to fully maintain the storage stability of a composition.

The compound for a catcher component may be sufficient as said compound. This invention may also relate to use (application) as a catcher component of the compound represented by General formula (1), or use (application) for manufacture of the catcher component of the compound represented by General formula (1).

Another aspect of the present invention provides a photocurable composition comprising the above compound and a photocurable resin component. The photocurable resin component may contain the monomer and photoinitiator which have a (meth)acryloyl group. According to such a photocurable composition, since the said compound is contained, water|moisture content is fully reduced, and it can utilize suitably for manufacture of the organic film mentioned later. Moreover, such a photocurable composition is excellent in storage stability.

Since said photocurable composition contains the said compound, a photocurable composition or its hardened|cured material can become useful also as a drying agent. The present invention may relate to use as a desiccant (application) or use (application) for the production of a desiccant of a composition containing the above compound and a photocurable resin component, or a cured product thereof.

Another aspect of the present invention provides a cured film comprising a cured product of the photocurable composition. In the cured film, the compound can be sufficiently dispersed in the cured film because, for example, the polymerizable unsaturated bond in the monomer having a (meth)acryloyl group is polymerized together with the polymerizable unsaturated bond in the compound described above. have. Therefore, the cured film can be a desiccant having excellent water-retaining properties.

Another aspect of the present invention provides an organic EL device. The organic EL element has an element substrate, a sealing substrate opposed to the element substrate, a sealing sealant for sealing the outer periphery of the element substrate and the sealing substrate, and a facing arrangement provided on the element substrate inside the sealing sealant A light emitting portion having a pair of electrodes and an organic layer provided between the pair of electrodes, and an alternately laminated sealing film comprising an inorganic film and an organic film provided so as to cover at least the surface of the light emitting portion. In the alternate lamination sealing film, the innermost film and the outermost film are inorganic films with respect to the light emitting portion. An organic film contains said photocurable composition or its hardened|cured material. The organic film may be the cured film described above.

ADVANTAGE OF THE INVENTION According to this invention, when applied to the composition containing a polymerizable monomer WHEREIN: The compound which can fully remove the water|moisture content in a composition and can fully maintain the storage stability of a composition is provided. Moreover, according to this invention, the photocurable composition containing such a compound is provided. Moreover, according to this invention, the cured film and organic electroluminescent element which used the photocurable composition are provided.

Fig. 1(a) is a schematic cross-sectional view showing one embodiment of an organic EL element, and Fig. 1(b) is a schematic cross-sectional view showing one embodiment of a light emitting part in the organic EL element.
Fig. 2(a) and Fig. 2(b) are schematic cross-sectional views showing another embodiment of the organic EL device.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail. However, this invention is not limited to the following embodiment.

In this specification, (meth)acrylate means an acrylate or a methacrylate corresponding thereto. The same applies to other analogous expressions such as (meth)acryloyl group.

[compound]

The compound of one Embodiment is a compound represented by following General formula (1).

In formula (1), M is a group 4 element of the periodic table, and represents a titanium atom, a zirconium atom, or a hafnium atom. As for M, a zirconium atom is preferable at the point which there is little coloring and the quality-change by an ultraviolet-ray also does not occur easily.

In Formula (1), R<^1> , R<^2> , R<^3>, and R<^4> respectively independently represent the alkyl group which may be substituted by the group containing a polymerizable unsaturated bond. Here, the alkyl group which may be substituted by the group containing a polymerizable unsaturated bond means an unsubstituted alkyl group, and the alkyl group substituted by the group containing a polymerizable unsaturated bond. The alkyl group substituted with a group containing a polymerizable unsaturated bond means an alkyl group in which any one or two or more hydrogen atoms of the unsubstituted alkyl group are substituted with a group containing a polymerizable unsaturated bond. The ^{groups represented by R 1} , R ² , R ³ and R ^{4 may} be the same or different, respectively.

Examples of the unsubstituted alkyl group include a linear, branched or cyclic alkyl group, and specifically, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group Tyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, no A nyl group, a decanyl group, a dodecanyl group, a tetradecanyl group, and a hexadecanyl group are mentioned. The number of carbon atoms of the unsubstituted alkyl group may be 1-28 or 1-8.

The group containing a polymerizable unsaturated bond may also contribute containing a C=C bond. As a group containing a C=C bond, a vinyl group, an allyl group, an allyloxy group, a (meth)acryloyl group, an alkynyl group etc. are mentioned, for example. The group containing a polymerizable unsaturated bond is at least 1 sort(s) or allyloxy group selected from the group which consists of a vinyl group, an allyl group, an allyloxy group, a (meth)acryloyl group, and an alkynyl group.

The alkyl group substituted with the group containing a polymerizable unsaturated bond WHEREIN: 2 or more may be sufficient as the number of substitution by group containing a polymerizable unsaturated bond. Examples of the alkyl group substituted with the group containing a polymerizable unsaturated bond include a group represented by the following formula (2-1), a group represented by the following formula (2-2), -CH ₂ -C-(CH ₂ -OOC- CH=CH ₂ ) ₃ group and the like. The alkyl group substituted with a group containing a polymerizable unsaturated bond has low self-polymerizability and is excellent in storage stability, so may be a group represented by the following formula (2-1) or a contribution represented by the following formula (2-2), It may also be a contribution represented by Formula (2-1).

In formulas (2-1) and (2-2), * represents a bond.

At least one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group substituted with a group containing a polymerizable unsaturated bond. All of R ¹ , R ² , R ³ and R ⁴ may be an alkyl group substituted with a group containing a polymerizable unsaturated bond. In this case, ^{the groups represented by R 1} , R ² , R ³ and R ^{4 may} be the same or different, but the same is preferable.

As for the compound of this embodiment, the compound represented by General formula (1) may be sufficient as ^{M is a zirconium atom, R<1>} , R<^2> , R<^3>, and R<^{4> are group represented by Formula (2-1).}

The compound of the present embodiment has excellent water-retaining properties. The present inventor estimates this reason as follows. That is, when a compound and water come into contact, the alkyloxy (alkoxy) group in the compound is substituted with a hydroxyl group derived from water, and water is introduced into the compound.

[Method for producing compound]

The compound of the present embodiment can be obtained by, for example, reacting a compound having a central atom of any one of a titanium atom, a zirconium atom, or a hafnium atom with an alcohol corresponding to an alkyl group substituted with a group containing a polymerizable unsaturated bond. .

The compound having a central atom of any one of a titanium atom, a zirconium atom, or a hafnium atom may be a compound in which an alkyloxy group (alkoxy group) corresponding to the above-described unsubstituted alkyl group is bonded to the central atom. Examples of the compound having a titanium atom include titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, titanium tetraoctoxide, and titanium tetradodecoxide. Examples of the compound having a zirconium atom include zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetrabutoxide, zirconium tetraoctoxide, and zirconium tetradodecoxide. Examples of the compound having a hafnium atom include hafnium tetraethoxide, hafnium tetrapropoxide, hafnium tetrabutoxide, hafnium tetraoctoxide, and hafnium tetradodecoxide.

The compound which has the central atom of any one of a titanium atom, a zirconium atom, or a hafnium atom may be used individually by 1 type, and may be used in combination of 2 or more type, However, It is preferable to use individually by 1 type.

The alcohol corresponding to the alkyl group substituted with the group containing a polymerizable unsaturated bond is, for example, an alcohol represented by the following formula (3-1), an alcohol represented by the following formula (3-2), pentaerythritol triacrylate, etc. can be heard Alcohol corresponding to the alkyl group substituted by the group containing a polymerizable unsaturated bond may be used individually by 1 type, and may be used in combination of 2 or more type.

In the compound represented by the general formula (1), the adjustment of the number of introduction of an alkyl group substituted with a group containing a polymerizable unsaturated bond is a compound having a central atom of any one of a titanium atom, a zirconium atom, or a hafnium atom, and polymerizable It can carry out by adjusting the ratio at the time of making the alcohol corresponding to the alkyl group substituted with the group containing an unsaturated bond react. The ^{compound represented by the general formula (1) in which all of R 1} , R ² , R ³ and R ⁴ has an alkyl group substituted with a group containing a polymerizable unsaturated bond is, for example, any one of a titanium atom, a zirconium atom, or a hafnium atom It can be obtained by reacting 4 or more equivalents of an alcohol corresponding to an alkyl group substituted with a group containing a polymerizable unsaturated bond with respect to a compound having one central atom.

Reaction conditions can be suitably selected according to the raw material compound used, raw material alcohol, etc. Reaction conditions can be adjusted, for example in the range of 0 degreeC - 150 degreeC of reaction temperature, and 0.5-48 hours of reaction time in the presence of a solvent or solvent. Moreover, you may distill off a volatile component under reduced pressure after completion|finish of reaction.

[Photocurable composition]

The photocurable composition of one Embodiment contains said compound and a photocurable resin component. The photocurable resin component may contain the monomer and photoinitiator which have a (meth)acryloyl group.

The monomer having a (meth)acryloyl group is not particularly limited as long as it has a (meth)acryloyl group. For example, a monofunctional (meth)acrylate compound having one (meth)acryloyl group, (meth) The polyfunctional (meth)acrylate compound etc. which have two or more acryloyl groups are mentioned. The photocurable composition of this embodiment is hardened|cured material by superposing|polymerizing the polymerizable unsaturated bond in the (meth)acryloyl group in the monomer which has a (meth)acryloyl group with the polymerizable unsaturated bond in a compound. can be formed.

Since the monomer which has a (meth)acryloyl group has the property that it is hard to melt|dissolve the organic layer of an organic electroluminescent element, it has a siloxane skeleton and may contain the monomer which has a (meth)acryloyl group. As such a monomer, methacryl modified silicone oil etc. are mentioned, for example. Methacryl-modified silicone oil means that methacryl (methacryloyl) groups are introduced into one end/both ends of the siloxane skeleton. Examples of the both-terminal methacrylic-modified silicone oil include silicones represented by the following general formula (4).

In formula (4), R<^5> represents a C1-C4 alkyl group each independently. Examples of R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. It is preferable that R<^5> is a methyl group.

In Formula (4), R<^6> represents a divalent organic group each independently. As a divalent organic group, a C1-C12 linear, branched or cyclic alkylene group etc. are mentioned, for example.

In Formula (4), n can be set so that a functional group equivalent (g/mol) may be set to 100-1000, for example.

A conventionally well-known thing can be used for methacryl modified silicone oil, Moreover, a commercial item can also be used as it is. As a suitable commercial item, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-2445, X-22-174ASX, X-22-2404 (product name) are, for example, , all of which are Shin-Etsu Chemical High School Co., Ltd.).

A photoinitiator will not be restrict|limited in particular, if it generate|occur|produces the active species which can be chain-polymerized by irradiating an active energy ray. At least 1 type selected from an ultraviolet-ray, an electron beam, and a visible light may be sufficient as an active energy ray, and an ultraviolet-ray may be sufficient as it. As a photoinitiator, a photoradical polymerization initiator etc. are mentioned, for example. Here, the active species capable of chain polymerization means that a polymerization reaction is initiated by reacting with a functional group capable of chain polymerization.

Examples of the photoradical polymerization initiator include benzoinketal, α-hydroxyketone, α-aminoketone, oxime ester, phosphine oxide, triarylimidazole dimer, benzophenone compound, quinone compound, benzoin ether. , a benzoin compound, a benzyl compound, an acridine compound, N-phenylglycine, coumarin, and the like.

0.1-10 mass parts, 0.3-5 mass parts, or 0.5-3 mass parts may be sufficient as content of a photoinitiator with respect to content 100 mass parts of the monomer which has a (meth)acryloyl group.

The photocurable resin component may contain other components other than the monomer which has a (meth)acryloyl group, and a photoinitiator. As another component, the sensitizer etc. for the purpose of improvement of sclerosis|hardenability and suppression of coloring of hardened|cured material are mentioned, for example. 0.1-20 mass parts may be sufficient as content of each component in another component, for example with respect to content 100 mass parts of the monomer which has a (meth)acryloyl group.

The content of the compound (compound represented by the general formula (1)) may be 0.1 parts by mass or more, 0.3 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more with respect to 100 parts by mass of the content of the photocurable resin component, 200 mass parts or less, 100 mass parts or less, 50 mass parts or less, or 20 mass parts or less may be sufficient. When content of a compound is 0.1 mass part or more with respect to content 100 mass parts of a photocurable resin component, there exists a tendency for a catchment capacity to become sufficient. When content of a compound is 200 mass parts or less with respect to content 100 mass parts of a photocurable resin component, there exists a tendency which can fully suppress a raise of a viscosity.

The photocurable composition may be an ink composition that can be applied. The photocurable composition can be applied, for example, to an inkjet coating method, a dispenser coating method, an ODF (One Drop Fill) method, a screen printing method, a spray method, a hot melt method, or the like. Since the photocurable composition is suitable for preparation of an organic film, the ink composition for inkjet application|coating may be sufficient as it. When applying to the coating method by an inkjet, 0.01-30 mPa*s may be sufficient as the viscosity in 25 degreeC of a photocurable composition.

A photocurable composition can be hardened (formed hardened|cured material) by irradiating an active energy ray. The conditions of active energy ray irradiation can be suitably adjusted according to the structural component of a photocurable composition. At least 1 type selected from an ultraviolet-ray, an electron beam, and a visible light may be sufficient as an active energy ray, and an ultraviolet-ray may be sufficient as it.

[Cured film]

The cured film of one Embodiment contains the hardened|cured material of a photocurable composition. In the cured film of this embodiment, since the polymerizable unsaturated bond in the monomer having a (meth)acryloyl group polymerizes with the polymerizable unsaturated bond in the compound, the compound is sufficiently dispersed in the cured film. can Therefore, the cured film can be a desiccant having excellent water-retaining properties.

[Organic EL device and its manufacturing method]

Fig. 1(a) is a schematic cross-sectional view showing one embodiment of an organic EL element, and Fig. 1(b) is a schematic cross-sectional view showing one embodiment of a light emitting part in the organic EL element. The organic EL element 100 shown in FIG. ), a sealing compound 6 for sealing the outer periphery, a light emitting part 20 provided on the element substrate 2 inside the sealing sealing compound 6, and at least the surface of the light emitting part 20. , an alternately laminated sealing film 12 composed of an inorganic film 8 and an organic film 10 . The light emitting part 20 shown in FIG.1(b) has a pair of electrodes (anode 22 and cathode 24) arranged oppositely, and the organic layer 26 provided between a pair of electrodes. In the alternate lamination sealing film 12 , the inorganic film 8 is the innermost film and the outermost film with respect to the light emitting part 20 . The organic film 10 contains the photocurable composition or a cured product thereof. The organic film 10 may be the cured film described above.

The number of laminated layers of the alternately laminated sealing film 12 composed of the inorganic film 8 and the organic film 10 is not particularly limited as long as the innermost film and the outermost film are inorganic films, and is 3, 5, 7 or 9 layers. It may be more than Moreover, as for the alternate lamination|stacking sealing film 12, if the surface of the light emitting part 20 is covered, the whole surface of the element substrate 2 inside the sealing sealing compound 6 does not necessarily need to be covered.

Although it does not restrict|limit especially as a material which comprises the inorganic film 8, Silicon compounds, such as silicon nitride (SiN), a silicon oxide (SiO), and nitrogen-containing silicon oxide (SiON), etc. are mentioned. The inorganic film 8 can normally be formed by chemical vapor deposition (CVD) of a constituent material. The thickness of the inorganic film 8 may be, for example, 0.1 to 3 µm.

The organic film 10 can be formed by producing the above-mentioned photocurable composition, a coating film on the inorganic film 8 by a normal inkjet method, irradiating the coating film with active energy rays to cure the photocurable composition. have. At least 1 type selected from an ultraviolet-ray, an electron beam, and a visible light may be sufficient as an active energy ray, and an ultraviolet-ray may be sufficient as it. The thickness of the organic film 10 may be, for example, 0.1 to 10 µm.

By repeatedly performing such an operation, the alternate lamination sealing film 12 can be obtained.

In the organic EL element 100 shown to Fig.1 (a), although hollow space remains inside the sealing sealing compound 6, hollow space does not necessarily exist, and all or part of hollow space is It may be sealed with a sealing material etc.

In the organic EL element 100, a conventionally known element can be applied to elements other than the alternately laminated sealing film 12 (especially the organic film 10), but an example thereof will be briefly described below.

The element substrate 2 is made of a rectangular glass substrate having insulation and light transmission properties, and on this element substrate 2, an anode 22 (electrode) is made of ITO (Indium Tin Oxide) as a transparent conductive material. is formed. The anode 22 is etched by a photoresist method with respect to an ITO film formed on the element substrate 2 by, for example, a PVD (Physical Vapor Deposition) method such as a vacuum deposition method or a sputtering method. It is formed by patterning into a predetermined pattern shape. A part of the anode 22 as an electrode is drawn out to the end of the element substrate 2 and connected to a drive circuit (not shown).

On the upper surface of the anode 22 , an organic layer 26 , which is a thin film containing an organic light emitting material, is laminated by, for example, a PVD method such as a vacuum vapor deposition method or a resistance heating method. The organic layer 26 may be formed in a single layer, or may be formed in the some layer from which a function differs. The organic layer 26 may have, for example, a four-layer structure in which a hole injection layer 26a, a hole transport layer 26b, a light emitting layer 26c, and an electron transport layer 26d are laminated in order from the anode 22 side. The hole injection layer 26a is formed of, for example, copper phthalocyanine (CuPc) having a film thickness of several 10 nm. The hole transport layer 26b is formed of, for example, bis[N-(1-naphthyl)-N-phenyl]benzidine (?-NPD) having a film thickness of several 10 nm. The light emitting layer 26c is formed of, for example, tris(8-quinolinolato)aluminum (Alq ₃ ) having a film thickness of several 10 nm. The electron transport layer 26d is formed of, for example, lithium fluoride (LiF) having a film thickness of several nm.

On the upper surface of the organic layer 26 (electron transport layer 26d), a cathode 24 (electrode), which is a metal thin film, is laminated by a PVD method such as a vacuum deposition method. Examples of the material of the metal thin film include simple metals having a small work function such as Al, Li, Mg, and In, and alloys having a small work function such as Al-Li and Mg-Ag. The cathode 24 is formed with a film thickness of, for example, several 10 nm to several 100 nm (preferably 50 nm to 200 nm). A part of the cathode 24 is drawn out to the end of the element substrate 2 and connected to a drive circuit (not shown).

The sealing substrate 4 is disposed so as to face the element substrate 2 with the organic layer 26 interposed therebetween. The outer peripheral portions of the element substrate 2 and the sealing substrate 4 are sealed with a sealing sealing compound 6 . As the sealing sealing compound 6, ultraviolet curable resin is mentioned, for example.

In the manufacturing method of the organic electroluminescent element of one Embodiment, the laminated body in which the light emitting part 20 which has the organic layer 26 etc. was formed on the element substrate 2 is prepared. On the other hand, by the above method, at least the light-emitting portion 20 is formed with an alternate lamination sealing film 12 composed of at least the inorganic film 8 , the organic film 10 , and the inorganic film 8 . Then, the sealing sealing compound 6 is apply|coated with the dispenser so that the desiccant apply|coated on the sealing board|substrate 4 may be enclosed. These operations may be performed in a glove box substituted with nitrogen at a dew point of -76°C or lower.

Next, the element substrate 2 on which the light emitting part 20 was mounted, and the sealing substrate 4 are bonded together, sandwiching the alternating laminated sealing film 12 and the sealing sealing compound 6 between them. The organic EL element 100 of this embodiment can be obtained by drying and/or hardening|curing a sealing sealing compound by ultraviolet irradiation and/or heating to the obtained structure as needed.

As mentioned above, although embodiment of this invention was described in detail, this invention is not limited to said embodiment. For example, in the said embodiment, although the organic electroluminescent element provided with the organic film which consists of a photocurable composition was illustrated, the said photocurable composition or its hardened|cured material (cured film) itself acts as a desiccant. In , this can be applied to a desiccant layer of an organic EL device having a desiccant layer. Fig. 2(a) and Fig. 2(b) are schematic cross-sectional views showing another embodiment of the organic EL device. The organic EL element 200 ( 300 ) shown in FIGS. 2A and 2B includes an element substrate 2 , a sealing substrate 4 opposed to the element substrate 2 ; The sealing sealing agent 6 which seals the outer periphery of the element substrate 2 and the sealing substrate 4, the light emitting part 20 provided on the element substrate 2 inside the sealing sealing compound 6, The sealing seal A desiccant layer 14 (16) comprising the above-described photocurable composition or a cured product thereof is provided on the inner side of the (6) light emitting part 20 . When the sealing sealing compound 6 seals the outer periphery of the element substrate 2 and the sealing substrate 4 , an airtight space is formed around the light emitting part 20 between the element substrate 2 and the sealing substrate 4 . is formed

The desiccant layer 14 in the organic EL element 200 shown to Fig.2 (a) is filling the airtight space around the light emitting part 20 inside the sealing sealing compound 6 . That is, the organic EL element 200 is an organic EL element having a so-called filling and sealing structure. However, the desiccant layer does not necessarily fill the entire airtight space in which the light emitting part 20 is provided. For example, like the organic electroluminescent element 300 shown to FIG.2(b), the desiccant layer 16 is formed on the sealing substrate 4, and hollow space remains inside the sealing sealing compound 6 there may be That is, the organic EL element 300 is an organic EL element having a so-called hollow sealing structure. In this case, the thickness of the desiccant layer 16 may be, for example, 1-300 micrometers. The desiccant layer 16 can be formed by apply|coating with methods, such as a dispenser.

In the organic EL elements 200 and 300 , a conventionally known element can be applied to elements other than the desiccant layers 14 and 16 .

In addition, the use of said photocurable composition or its hardened|cured material (cured film) is not necessarily limited to an organic electroluminescent element, For example, it can apply also to the display apparatus (quantum dot display) etc. which used quantum dots. More specifically, for example, in the color filter of a quantum dot display, it can use also as an organic film (desiccant layer) etc. for covering the surface.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these Examples.

[Synthesis of compound (capture component)] (Example 1)

In a flask, trimethylol propane diallyl ether (2,2-bis(allyloxymethyl)-1-butanol, a compound represented by the formula (3-1)) (trade name: Neoallyl T-20, Osaka Co., Ltd.) Soda) 21 mass parts and 10 mass parts of zirconium tetrapropoxide (Tokyo Kasei Kogyo Co., Ltd.) were thrown in, and it stirred at 25 degreeC for 1 hour. Thereafter, the volatile components and the like were distilled off under reduced pressure at 60° C. and 300 Pa for 3 hours, and then the volatile components and the like were distilled off under reduced pressure at 150° C. and 300 Pa for 3 hours to obtain the compound of Example 1 as a transparent viscous substance. The compound of Example 1 was zirconium tetrakis(2,2-bis(allyloxymethyl)-1- butoxide), ie, R ¹ , R ² , R ³ and R ⁴ in Formula (1) are all presumed to be zirconium compounds which are 2,2-bis(allyloxymethyl)-1-butyl groups.

(Comparative Example 1)

To a flask, 28 parts by mass of trimethylol propane diallyl ether (2,2-bis(allyloxymethyl)-1-butanol) (trade name: Neoallyl T-20, Osaka Soda Co., Ltd.) and aluminum sec-butyl 10 parts by mass of a rate (trade name: ADBD, Kawaken Fine Chemicals Co., Ltd.) was charged and stirred at 25°C for 1 hour. Thereafter, the volatile components and the like were distilled off under reduced pressure at 60° C. and 300 Pa for 3 hours, and the volatile components and the like were distilled off under reduced pressure for 3 hours at 150° C. and 300 Pa again, and the compound of Comparative Example 1 as an ultra-high viscosity transparent viscous substance got The compound of Comparative Example 1 was aluminum tris(2,2-bis(allyloxymethyl)-1-butoxide in that 3 equivalents of trimethylol propane diallyl ether were reacted with respect to aluminum sec-butylate. ) is assumed to be

[Capture test]

The compound of Example 1 by adding the compound of Example 1 to a monomer having a (meth)acryloyl group, and measuring the water content contained in the monomer having a (meth)acryloyl group before and after the addition by the Karl Fischer method of the water catchment test was performed. As the monomer having a (meth)acryloyl group, both-terminal methacrylic modified silicone oil X-22-164 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 25°C viscosity: 10 mPa·s) was used. As the measuring device, a trace moisture measuring device (KF method moisture meter, trade name: CA-100, Mitsubishi Chemical Analytech Co., Ltd.) was used. As a result of vacuum degassing of X-22-164 and measuring the moisture content, it was found to be 136.8 ppm. Next, 10 mass parts of the compound of Example 1 was thrown in with respect to 100 mass parts of X-22-164, and it was left to stand at 25 degreeC for 1 hour. Thereafter, X-22-164 containing the compound of Example 1 was vacuum degassed, and as a result of measuring the moisture content, it was 0 ppm (less than the detection limit). From this, it was confirmed that the compound of Example 1 can fully remove the water|moisture content contained in the monomer which has a (meth)acryloyl group.

[Storage stability test]

The compound shown in Table 1, the monomer which has a (meth)acryloyl group, and the photoinitiator were mixed by content (unit: mass part) shown in Table 1, and the composition for the test of Test Examples 1-4 was prepared. In addition, "Irgacure 907" in Table 1 is 2-[4(methylthio)benzoyl]-2-(4-morpholinyl)propane (made by BASF, the same hereinafter). Each composition for a test was preserve|saved under the conditions of 25 degreeC or 60 degreeC, and the presence or absence of generation|occurrence|production of the quality change in the composition for a test was visually confirmed. A result is shown in Table 1. Moreover, the viscosity in 25 degreeC was measured before and behind storage about the composition for tests of Test Examples 1 and 2 in which the generation|occurrence|production of a quality change did not occur. A result is shown in Table 1.

[Table 1]

As shown in Table 1, in Test Examples 3 and 4 using the compound of Comparative Example 1, generation of deterioration in the composition for testing was observed after storage, whereas in Test Examples 1 and 2 using the compound of Example 1, after storage. Also, the generation|occurrence|production of the quality change in the composition for a test was not observed. In addition, in Test Examples 1 and 2, there was little change in the viscosity before and after storage. From these points, it was confirmed that the compound of Example 1 is capable of sufficiently maintaining the storage stability of the composition for testing.

[Preparation of photocurable composition] (Example 2)

Into a flask, 12 parts by mass of both-terminal methacrylic modified silicone oil X-22-164AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., 25°C viscosity: 12 mPa·s), 1 part by mass of the compound of Example 1, and 0.1 Irgacure 907 of a mass part was thrown in, and it stirred at 25 degreeC for 1 hour. Then, volatile components etc. were distilled off at 100 degreeC for 1 hour, and the photocurable composition (ink composition) of Example 2 was obtained as a transparent liquid. The viscosity in 25 degreeC of the photocurable composition of Example 2 was 17.1 mPa*s.

[Review of applicability and catchability]

By manufacturing the organic EL element for a test and apply|coating the photocurable composition of Example 2 to this, the applicability|paintability and water holding property of the photocurable composition were examined simply.

(Production of organic EL device)

ITO of the electrically-conductive material which has transparency was formed into a film with the film thickness of 140 nm on the element substrate by the sputtering method. The film of ITO was patterned into a predetermined pattern shape by etching by a photoresist method to form an anode.

A hole injection layer is formed on the upper surface of the formed anode by depositing copper phthalocyanine (CuPc) to a film thickness of 70 nm by a resistance heating method, and bis[N-(1-naphthyl) is formed on the upper surface of the hole injection layer. A hole transporting layer is formed by forming -N-phenyl]benzidine (α-NPD) to a film thickness of 30 nm, and tris(8-quinolinolato)aluminum (Alq ₃ ) is formed on the upper surface of the hole transporting layer to a film thickness of 50 nm. Thus, a light emitting layer was formed.

Further, lithium fluoride (LiF) was formed on the upper surface of the light emitting layer to a thickness of 7 nm to form an electron transport layer, and aluminum as a cathode was physically vapor deposited on the surface of the electron transport layer to a thickness of 150 nm. As described above, a laminate in which an anode, an organic layer (hole injection layer/hole transport layer/light emitting layer/electron transport layer) and a cathode are laminated in this order was formed on the element substrate.

Next, in a glove box substituted with nitrogen at a dew point of -76° C. or less, the photocurable composition of Example 2 was applied to the central portion of the sealing substrate by ODF, and cured by UV irradiation, and the photocurable composition of Example 2 An organic film containing the cured product of the composition was formed. The sealing sealing compound which consists of ultraviolet curable resin was apply|coated on the sealing board|substrate with the dispenser so that an organic film might be surrounded.

Then, the element substrate and the sealing substrate were bonded together in the direction used as a laminated body, an organic film, and sealing sealing compound inside. In that state, the outer periphery of the element substrate and the sealing substrate were sealed by ultraviolet irradiation and heating at 80°C, and the organic EL element of the hollow sealing structure in which the organic film was provided in the hermetic space enclosed by the sealing sealing compound was obtained.

(change in luminous area ratio)

The obtained organic electroluminescent element was left to stand in the high-temperature, high-humidity environment of 85 degreeC and 85 %RH for 1250 hours. It was found that there was almost no change in the light emission area ratio before and after the test, the photocurable composition of Example 2 was excellent in applicability, and the organic film formed also had sufficient water-retaining properties.

2… device substrate
4… sealing substrate
6… sealing sealant
8… inorganic membrane
10… organic film
12… Alternating Lamination Sealing Film
14, 16… desiccant layer
20… light emitting part
22… anode
24… cathode
26… organic layer
26a… hole injection layer
26b... hall transport floor
26c… light emitting layer
26d… electron transport layer
100, 200, 300… organic EL device

Claims (5)

The compound represented by the following general formula (1).

[In formula (1), M represents a titanium atom, a zirconium atom or a hafnium atom, and R ¹ , R ² , R ³ and R ⁴ each independently represent an optionally substituted alkyl group containing a polymerizable unsaturated bond. . However, ^{at least one of R 1} , R ² , R ³ and R ⁴ is an alkyl group substituted with a group containing a polymerizable unsaturated bond.] The photocurable composition containing the compound of Claim 1, and a photocurable resin component. 3. The method according to claim 2,
The said photocurable resin component, the photocurable composition containing the monomer which has a (meth)acryloyl group, and a photoinitiator. The cured film containing the hardened|cured material of the photocurable composition of Claim 2 or 3. a device substrate;
a sealing substrate disposed opposite to the element substrate;
a sealing sealing agent for sealing the outer periphery of the element substrate and the sealing substrate;
a light emitting part provided on the element substrate inside the sealing sealant and having a pair of electrodes disposed opposite to each other and an organic layer provided between the pair of electrodes;
An alternate lamination sealing film made of an inorganic film and an organic film is provided to cover at least the surface of the light emitting part,
In the alternate lamination sealing film, the innermost film and the outermost film are inorganic films with respect to the light emitting part,
The said organic film is an organic electroluminescent element containing the photocurable composition of Claim 2 or 3, or its hardened|cured material.

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