JP2020012048A - Ultraviolet curable resin composition, method for producing organic el light emitting device and organic el light emitting device - Google Patents

Abstract

To provide an ultraviolet curable resin composition that contains a moisture absorbent but can prevent the reduced transparency of a cured product caused by the moisture absorbent and can also prevent the increased viscosity and reduced storage stability caused by the moisture absorbent.SOLUTION: An ultraviolet curable resin composition contains an acryl compound (A), a photopolymerization initiator (B), a moisture absorbent with an average particle size of 200 nm or less (C), and a dispersant (D) having two or more adsorption groups in one molecule.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an ultraviolet-curable resin composition, a method for manufacturing an organic EL light-emitting device, and an organic EL light-emitting device, and more specifically, an ultraviolet-curable resin composition suitable for producing a sealing material in an organic EL light-emitting device, The present invention relates to a method for manufacturing an organic EL light emitting device using the ultraviolet curable resin composition, and an organic EL light emitting device including the sealing material.

  Organic EL light-emitting devices are applied to lighting, displays, and the like, and are expected to spread in the future.

  Among the organic EL light-emitting devices, a device called a top emission type has, for example, an organic EL element arranged on a support substrate, a transparent substrate arranged so as to face the support substrate, and a transparent substrate between the support substrate and the transparent substrate. It is configured by filling a suitable sealing material. In this case, light emitted from the organic EL element passes through the sealing material and the transparent substrate and exits to the outside.

  The sealing material suppresses the intrusion of moisture into the organic EL element, thereby suppressing the generation and growth of dark spots in the organic EL element. The dark spot is a portion that does not emit light and is generated when the organic EL element is deteriorated by moisture.

  In some cases, merely providing a sealing material in the organic EL light emitting device may not sufficiently prevent moisture from entering. Therefore, a hygroscopic agent is provided between the supporting substrate and the transparent substrate. However, a process for providing the hygroscopic agent is required, which complicates the structure of the organic EL light emitting device and lowers the manufacturing efficiency. I will.

  It has also been proposed to add a hygroscopic agent to a composition for producing a sealing material to impart hygroscopicity to the sealing material. For example, Patent Document 1 discloses a sealant for an organic electroluminescent display element containing a radically polymerizable compound, a polymerization initiator and / or a curing agent, and a powdery molecular sieve.

JP-A-2012-012559

  Simply dispersing a hygroscopic agent in the sealing material as disclosed in Patent Literature 1 causes a decrease in the transparency of the sealing material, and lowers the luminous efficiency of the organic EL light emitting device. . If the particle size of the hygroscopic agent is reduced, the transparency can be expected to be improved, but the moldability is deteriorated due to an increase in the viscosity of the composition for producing the sealing material. If the particle size of the hygroscopic agent is small, the hygroscopic agent is likely to aggregate during storage of the composition, so that the storage stability deteriorates.

  An object of the present invention is to provide an ultraviolet curable resin composition in which a moisture absorbent hardly reduces the transparency of a cured product while containing a moisture absorbent, and hardly causes an increase in viscosity and a decrease in storage stability due to the moisture absorbent. An object of the present invention is to provide a method for manufacturing an organic EL light emitting device using the ultraviolet curable resin composition, and an organic EL light emitting device provided with a sealing material made of a cured product of the ultraviolet curable resin composition.

  The ultraviolet curable resin composition according to one embodiment of the present invention includes an acrylic compound (A), a photopolymerization initiator (B), a hygroscopic agent (C) having an average particle size of 200 nm or less, and two or more in one molecule. It contains a dispersant (D) having an adsorptive group.

  A method for manufacturing an organic EL light-emitting device according to one embodiment of the present invention is a method for manufacturing an organic EL light-emitting device including an organic EL element and a sealing material covering the organic EL element, wherein the ultraviolet-curable resin composition And forming the encapsulant by irradiating the ultraviolet curable resin composition with ultraviolet rays and curing the molded article by an inkjet method.

  An organic EL light emitting device according to one embodiment of the present invention includes an organic EL element and a sealing material covering the organic EL element, and the sealing material is a cured product of the ultraviolet curable resin composition.

  In one embodiment of the present invention, an ultraviolet curable resin composition in which a moisture absorbent hardly reduces the transparency of a cured product while containing a moisture absorbent, and hardly causes an increase in viscosity and a decrease in storage stability due to the moisture absorbent. There is an advantage that an organic EL light emitting device including a product, a method of manufacturing an organic EL light emitting device using the ultraviolet curable resin composition, and a sealing material made of a cured product of the ultraviolet curable resin composition can be obtained.

FIG. 1 is a schematic cross-sectional view illustrating a first example of an organic EL light emitting device according to an embodiment of the present invention. FIG. 4 is a schematic sectional view showing a second example of the organic EL light emitting device according to the embodiment of the present invention.

  Hereinafter, an embodiment of the present invention will be described.

  The ultraviolet-curable resin composition (hereinafter, also referred to as composition (X)) according to the present embodiment includes an acrylic compound (A), a photopolymerization initiator (B), a hygroscopic agent (C) having an average particle diameter of 200 nm or less, And a dispersant (D) having two or more adsorptive groups in one molecule. Since the average particle size of the hygroscopic agent (C) is 200 nm or less, the hygroscopic agent (C) does not easily lower the transparency of the cured product of the composition (X). Furthermore, since the dispersant (D) has two or more adsorption groups in one molecule, the desiccant (C) can be favorably dispersed in the composition (X) and the cured product. Therefore, in the composition (X), an increase in viscosity and a decrease in storage stability due to the hygroscopic agent (C) hardly occur.

  The viscosity at 25 ° C. of the composition (X) is preferably from 1 mPa · s to 30 mPa · s. In this case, the composition (X) can be easily molded at a room temperature by a method such as a casting method, and the composition (X) can also be molded by an inkjet method. The viscosity is more preferably 20 mPa · s or less, and even more preferably 15 mPa · s or less. It is also preferable that this viscosity is 5 mPa · s or more.

  It is also preferable that the viscosity at 40 ° C. of the composition (X) is from 1 mPa · s to 30 mPa · s. In this case, even if the viscosity of the composition (X) at room temperature is any value, it is possible to lower the viscosity by slightly heating the composition (X). Therefore, when heated, the composition (X) can be easily formed by a method such as a casting method, and the composition (X) can be formed by an ink jet method. Further, since the viscosity of the composition (X) can be reduced without greatly heating the composition (X), the composition of the composition (X) is less likely to change due to volatilization of components in the composition (X). The viscosity is more preferably 20 mPa · s or less, and even more preferably 15 mPa · s or less. It is also preferable that this viscosity is 5 mPa · s or more.

The viscosity of the composition (X) is measured using a rheometer at a shear rate of 100 s ^-1 . As the rheometer, for example, model number DHR-2 manufactured by Anton Paar Japan can be used.

  Such a low viscosity at 25 ° C. or 40 ° C. of the composition (X) can be achieved by the composition of the composition (X) described in detail below.

  When the thickness of the cured product of the composition (X) is 10 μm, the total light transmittance is preferably 90% or more. In this case, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, the extraction efficiency of light that passes through the sealing material 5 and is emitted to the outside can be particularly improved. The light transmittance of such a cured product can also be achieved by the composition of the composition (X) described in detail below.

  Hereinafter, the present embodiment will be described in more detail.

1. First, the structure of the organic EL light emitting device will be described. The organic EL light emitting device 1 includes an organic EL element 4 and a sealing material 5 that covers the organic EL element 4. The sealing material 5 may cover the organic EL element 4 in a state of being in direct contact with the organic EL element 4, or may be configured to cover the organic EL element 4 with any layer interposed between the sealing material 5 and the organic EL element 4. May be covered. Note that EL is an abbreviation for electroluminescence. Further, the organic EL element 4 is also called an organic light emitting diode.

  A first example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. This organic EL light emitting device 1 is a top emission type. The organic EL light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at an interval, an organic EL element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and the support substrate 2. A sealing material 5 is provided between the transparent substrate 3 and the transparent substrate 3. In the first example, the organic EL light emitting device 1 includes a passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the organic EL element 4. That is, the passivation layer 6 is interposed between the organic EL element 4 and the sealing material 5 covering the organic EL element 4.

  The support substrate 2 is made of, for example, a resin material, but is not limited to this. The transparent substrate 3 is made of a light-transmitting material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The organic EL element 4 includes, for example, a pair of electrodes and an organic light emitting layer between the electrodes. The organic light emitting layer includes, for example, a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron transport layer, and these layers are stacked in the order described above. Although only one organic EL element 4 is shown in FIG. 1, the organic EL light emitting device 1 includes a plurality of organic EL elements 4, and the plurality of organic EL elements 4 form an array on the support substrate 2. It may be configured. The passivation layer 6 is preferably made of silicon nitride or silicon oxide.

  A second example of the structure of the organic EL light emitting device 1 will be described with reference to FIG. Elements common to those in the first example shown in FIG. 1 are denoted by the same reference numerals as in FIG. 1, and detailed description will be omitted as appropriate. The organic EL light emitting device 1 shown in FIG. 2 is also a top emission type. The organic EL light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 at an interval, an organic EL element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and an organic EL element 4. Is provided.

  As in the case of the first example, the organic EL element 4 includes, for example, a pair of electrodes 41 and 43 and an organic light emitting layer 42 between the electrodes 41 and 43. The organic light emitting layer 42 includes, for example, a hole injecting layer 421, a hole transporting layer 422, an organic light emitting layer 423, and an electron transporting layer 424, and these layers are stacked in the order described above.

  The organic EL device 1 includes a plurality of organic EL elements 4, and the plurality of organic EL elements 4 form an array 9 (hereinafter, referred to as an element array 9) on the support substrate 2. The element array 9 also includes the partition wall 7. The partition 7 is on the support substrate 2 and partitions between two adjacent organic EL elements 4. The partition 7 is produced by, for example, molding a photosensitive resin material by a photolithography method. The element array 9 also includes connection wirings 8 for electrically connecting the electrodes 43 and the electron transport layers 424 of the adjacent organic EL elements 4. The connection wiring 8 is provided on the partition wall 7.

  The organic EL light emitting device 1 also includes a passivation layer 6 that covers the organic EL element 4. The passivation layer 6 is preferably made of silicon nitride or silicon oxide. Passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the organic EL element 4 by covering the element array 9 in a state of being in direct contact with the element array 9. The second passivation layer 62 is disposed at a position opposite to the element array 9 with respect to the first passivation layer 61, and a space is provided between the second passivation layer 62 and the first passivation layer 61. ing. The sealing material 5 is filled between the first passivation layer 61 and the second passivation layer 62. That is, the first passivation layer 61 is interposed between the organic EL element 4 and the sealing material 5 covering the organic EL element 4.

  Further, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is made of, for example, a transparent resin material. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 may be the same as or different from that of the sealing material 5.

  The sealing material 5 in the organic EL light emitting device 1 having the structure exemplified above can be made from the ultraviolet curable resin composition according to the present embodiment. That is, the ultraviolet curable resin composition is used for producing the sealing material 5 for the organic EL element 4. In other words, the ultraviolet curable resin composition is preferably a composition for producing a sealing material, a composition for sealing an organic EL element, or a composition for producing an organic EL light emitting device.

2. UV curable resin composition The UV curable resin composition (hereinafter, also referred to as composition (X)) will be described.

  As described above, the composition (X) has an acrylic compound (A), a photopolymerization initiator (B), a hygroscopic agent (C) having an average particle diameter of 200 nm or less, and two or more adsorbing groups in one molecule. Contains a dispersant (D). When the composition (X) is irradiated with ultraviolet rays, a photo-radical polymerization reaction is initiated by the photo-radical polymerization initiator (B) to cure the acrylic compound (A), whereby a cured product can be produced. The components of the composition (X) are described in more detail below.

  As described above, the composition (X) contains the acrylic compound (A). The acrylic compound (A) has one or more (meth) acryloyl groups in one molecule.

  The viscosity at 25 ° C. of the entire acrylic compound (A) is preferably 50 mPa · s or less. In this case, the acrylic compound (A) can make the composition (X) particularly low in viscosity. The viscosity of the entire acrylic compound (A) is more preferably 30 mPa · s or less, particularly preferably 20 mPa · s or less. Further, the viscosity of the entire acrylic compound (A) is, for example, 3 mPa · s or more.

  It is also preferable that the viscosity at 40 ° C. of the entire acrylic compound (A) is 50 mPa · s or less. In this case, the acrylic compound (A) can particularly lower the viscosity of the composition (X) when heated. The viscosity of the entire acrylic compound (A) is more preferably 30 mPa · s or less, particularly preferably 20 mPa · s or less. The viscosity of the entire acrylic compound (A) is, for example, 3 mPa · s or more.

  The compound which the acrylic compound (A) may contain will be described.

  The acrylic compound (A) preferably contains a polyfunctional acrylic compound (A1) having two or more (meth) acryloyl groups in one molecule. In this case, the polyfunctional acrylic compound (A1) can increase the glass transition temperature of the cured product, and therefore, can improve the heat resistance of the cured product and the sealing material 5. The amount of the polyfunctional acrylic compound (A1) is preferably 50% by mass or more and 100% by mass or less based on the whole acrylic compound (A). The acrylic compound (A) may contain only the polyfunctional acrylic compound (A1).

  Examples of the polyfunctional acrylic compound (A1) include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentatriester tetra Acrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate , Tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, propoxylated (3) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate Ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, hexadiol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, Bispentaerythritol hexaacrylate, ethylene glycol diacrylate 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, -N-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol diacrylate hydroxypivalate, trimethylolpropane triacrylate hydroxypivalate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate , Neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, tetramethylolpropane triacrylate Rate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di ( Meta Acrylate, containing at least one compound selected ethoxylated trimethylolpropane triacrylate, and from the group consisting of propoxylated trimethylol propane triacrylate.

  The acrylic equivalent of the polyfunctional acrylic compound (A1) is preferably 150 g / eq or less, more preferably 90 g / eq or more and 150 g / eq or less. The weight average molecular weight of the polyfunctional acrylic compound (A1) is, for example, 100 or more and 1000 or less, and more preferably 200 or more and 800 or less.

  The polyfunctional acrylic compound (A1) preferably contains a compound having at least one of a benzene ring, an alicyclic ring and a polar group. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, shrinkage when the composition (X) is cured can be particularly reduced. Further, the adhesion between the cured product and the member made of the inorganic material can be enhanced. The polyfunctional acrylic compound (A1) is especially selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, trimethylolpropane triacrylate and pentatriestole tetraacrylate. It is preferable to contain at least one compound. These compounds can particularly reduce shrinkage when the composition (X) is cured. Further, these compounds can also enhance the adhesion between the cured product and the member made of an inorganic material.

  The acrylic compound (A) also preferably contains a monofunctional acrylic compound (A2) having only one (meth) acryloyl group in one molecule. The monofunctional acrylic compound (A2) can suppress shrinkage of the composition (X) during curing.

  The amount of the monofunctional acrylic compound (A2) based on the total amount of the acrylic compound (A) is preferably more than 0% by mass and 50% by mass or less. When the amount of the monofunctional acrylic compound (A2) is more than 0% by mass, shrinkage of the composition (X) during curing can be suppressed. In addition, when the amount of the monofunctional acrylic compound (A2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (A1) can be 50% by mass or more. Can be particularly improved. The content of the monofunctional acrylic compound (A2) is more preferably 5% by mass or more, and further preferably 30% by mass or less.

  The monofunctional acrylic compound (A2) is, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate , Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, Imido acrylate, isoamyl acrylate, ethoxylated succinic acid Acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5- Trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nilphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, phenoxy Ethyl acrylate, cyclohexyl (meta A) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylation Tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloylmorpholine, isobornyl acrylate, dicyclopentanyl acrylate, Phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, - cyclohexanedimethanol monoacrylate, containing at least one compound selected from the group consisting of 3-methacryloyloxy methyl cyclohexene oxide, and 3-acryloyloxy methyl cyclohexene oxide.

  The monofunctional acrylic compound (A2) may contain at least one compound selected from the group consisting of a compound having an alicyclic structure and a compound having a cyclic ether structure.

  Compounds having an alicyclic structure include, for example, phenoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butyl Cyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, Acryloyl morpholine, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethyl Glycol acrylate, containing at least one compound selected from the group consisting of 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate.

  The number of ring members of the cyclic ether structure in the compound having a cyclic ether structure is preferably 3 or more, more preferably 3 or more and 4 or less. The number of carbon atoms contained in the cyclic ether structure is preferably 2 or more and 9 or less, more preferably 2 or more and 6 or less. The compound having a cyclic ether structure contains, for example, at least one compound selected from the group consisting of 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

  The acrylic compound (A) preferably contains a component (a) composed of at least one compound having a viscosity at 25 ° C. of 20 mPa · s or less. In this case, the component (a) can lower the viscosity of the composition (X). The compound contained in the component (a) may be a compound contained in the polyfunctional acrylic compound (A1), or may be a compound contained in the monofunctional acrylic compound (A2).

  The ratio of the component (a) to the total amount of the acrylic compound (A) is preferably from 50% by mass to 100% by mass. In this case, the viscosity of the composition (X) can be particularly reduced, and the composition (X) can be particularly easily applied by an inkjet method. The ratio of the component (a) is more preferably 60% by mass or more, and further preferably 70% by mass or more. Further, the ratio of the component (a) is more preferably 95% by mass or less, and further preferably 90% by mass or less.

  Component (a) preferably contains a compound having a glass transition temperature of 80 ° C. or higher. That is, the component (a) preferably contains a compound having a viscosity at 25 ° C of 20 mPa · s or less and a glass transition temperature of 80 ° C or more. In this case, the component (a) can increase the glass transition temperature of the cured product while lowering the viscosity of the composition (X). Component (a) more preferably contains a compound having a glass transition temperature of 90 ° C. or higher, and even more preferably contains a compound having a glass transition temperature of 100 ° C. or higher. The upper limit of the glass transition temperature of the compound contained in the component (a) is not limited, but is, for example, 150 ° C. or lower.

  Component (a) is, for example, a group consisting of isobornyl acrylate, dicyclopentanyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. At least one compound selected from the group consisting of:

  The acrylic compound (A) contains a component (b) composed of a compound having at least one skeleton selected from the group consisting of a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. Is also good. Component (b) can enhance the adhesion between the cured product and the member made of an inorganic material. The compound contained in the component (b) may be a compound contained in the polyfunctional acrylic compound (A1) or a compound contained in the monofunctional acrylic compound (A2). The compound contained in the component (b) may be a compound contained in the component (a).

  The ratio of the component (b) to the total amount of the acrylic compound (A) is preferably 5% by mass or more and 50% by mass or less. When the proportion of the component (b) is 5% by mass or more, the adhesion of the cured product is further increased. In addition, when the proportion of the component (b) is 50% by mass or less, the maximum peak value of the composition (X) can be reduced, and the viscosity of the composition (X) is further reduced to reduce the composition (X). Can be easily formed by an inkjet method. The ratio of the component (b) is more preferably 30% by mass or more, and further preferably 40% by mass or less. Note that the acrylic compound (A) may not contain the component (b), and in this case, the maximum peak value of the composition (X) can be particularly low.

  Component (b) can contain, for example, at least one compound selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, and bisphenol F polyethoxy diacrylate.

  The acrylic compound (A) is a compound represented by the following formula (100), at least one component selected from the group consisting of morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate (c) ) Is also preferable. By the component (c), the sealing material 5 made of the composition (X) can be provided with adhesion to a member made of an inorganic material such as the passivation layer 6. The compound contained in the component (c) may be a compound contained in the component (a).

In the formula (100), R ⁰ is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of the R ¹ R ¹¹ is H, alkyl or -R ¹² -OH, R ¹² is at least one of R ¹¹ from it and R ¹ is an alkylene group which is an alkyl group or -R ¹² -OH. R ¹ to R ¹¹ are not chemically bonded to each other.

  When X is a divalent hydrocarbon group, X preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms. The divalent hydrocarbon group is, for example, a methylene group, an ethylene group or a propylene group. It is particularly preferable that X is a single bond or a methylene group. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

When at least one of R ¹ to R ¹¹ is an alkyl group, the alkyl group preferably has 1 to 8 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. The alkyl group may be linear and have a branch. That is, for example, when the alkyl group is a butyl group, the butyl group may be a t-butyl group, an n-butyl group, or a sec-butyl group. When the alkyl group is a hexyl group, the hexyl group may be a t-hexyl group, an n-butyl group, or a sec-butyl group. When the alkyl group is an octyl group, the octyl group may be, for example, a t-octyl group. It is particularly preferred if the alkyl group is a methyl group or a t-butyl group. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

In the formula (100), it is preferable that an alkyl group or —R ¹² —OH is connected to only the 4-position of the cyclohexane ring. That is, among R ¹ to R ¹¹ , it is preferable that at least one of R ⁶ and R ⁷ is an alkyl group or —R ¹² —OH, and the rest are each H. It is particularly preferred that, of R ¹ to R ¹¹ , only R ⁶ is an alkyl group or —R ¹² —OH, and the rest are each H. In this case, the compound represented by the formula (100) can have good reactivity, and particularly easily gives the sealing material 5 adhesion to a member made of an inorganic material. This is because that has a conformation of the cyclohexane ring is boat-shaped in the compound represented by the formula (100), and bulky alkyl group or -R ¹² -OH at the 4-position is easily located pseudo equatorial position it is conceivable that. It is considered that when the compound represented by the formula (100) has such a structure, the reactivity of the (meth) acryloyl group in the compound represented by the formula (100) is increased. When the compound represented by the formula (100) has such a structure, the compound represented by the formula (1) can increase the free volume in the sealing material 5. Therefore, it is considered that the interface free energy between the sealing material 5 and the member made of the inorganic material tends to be small, and therefore, the adhesion between the sealing material 5 and the member made of the inorganic material tends to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example it is preferable alkyl group or -R ¹² -OH is a t- butyl group.

In the formula (100), it is also preferable that an alkyl group or —R ¹² —OH is connected to each of only the 3- and 5-positions of the cyclohexane ring. That is, among R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, and at least one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, It is preferred that each of the remaining is H. Of R ¹ to R ¹¹ , only one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, and at least one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH; More preferably, each is H. Of R ¹ to R ¹¹ , at least one of R ⁴ and R ⁵ is an alkyl group or —R ¹² —OH, only one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, and the remaining More preferably, each is H. Also in this case, the compound represented by the formula (100) can have good reactivity, and particularly easily gives the sealing material 5 adhesion to a member made of an inorganic material. This means that the cyclohexane ring in the compound represented by the formula (100) has a boat-shaped conformation, and the bulky alkyl group or —R ¹² —OH at each of the 3- and 5-positions is located at the pseudo-equatorial position. It is thought that it is easy. For this, as in the case where only the 4-position of the cyclohexane ring is an alkyl group or -R ¹² -OH connected, reactive (meth) acryloyl group in the compound represented by the formula (100) is increased, and It is considered that the adhesion between the sealing material 5 and the member made of the inorganic material is likely to be high. The higher the bulk alkyl group or -R ¹² -OH, alkyl or -R ¹² -OH is likely located in pseudo equatorial position. From this point of view, it is preferable that preferably larger the number of carbon atoms in the alkyl group or -R ¹² -OH, also an alkyl group or -R ¹² -OH and a branch. For example it is preferable alkyl group or -R ¹² -OH is a t- butyl group.

When at least one of R ¹ to R ¹¹ is —R ¹² —OH, the carbon number of R ¹² is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less. R ¹² is, for example, a methylene group, an ethylene group or a propylene group. Particularly preferably, R ^{12 is a} methylene group. In this case, there is an advantage that the compound (A1) has a small molecular weight and a low viscosity.

In the formula (100), it is particularly preferable that each of R ¹ to R ¹¹ is H or an alkyl group, and at least one of R ¹ to R ¹¹ is an alkyl group. In this case, the compound represented by the formula (100) can have a particularly low viscosity, so that the composition (X) can have a particularly low viscosity. Therefore, the composition (X) is particularly easily formed by the ink jet method.

  The component (c) preferably contains at least one compound selected from the group consisting of a compound represented by the following formula (110), a compound represented by the following formula (120), and a compound represented by the following formula (130). In this case, shrinkage when the composition (X) is cured can be particularly reduced. Further, these compounds can also particularly enhance the adhesion between the cured product and the member made of an inorganic material.

  It is particularly preferable that the compound (A1) contains at least one of the compound represented by the formula (110) and the compound represented by the formula (120). In this case, the viscosity of the composition (X) is particularly easily reduced, the glass transition temperature of the sealing material 5 is particularly easily increased, and the adhesion between the sealing material 5 and a member made of an inorganic material is particularly easily increased. Further, since the compound represented by the formula (110) and the compound represented by the formula (120) are hard to volatilize, the storage stability of the composition (X) is easily improved.

  It is also preferred that compound (A1) contains at least one component selected from the group consisting of morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. Since these compounds contain nitrogen, they have good affinity with the inorganic material, and therefore, it is particularly easy to increase the adhesion between the sealing material 5 and the member made of the inorganic material. In addition, the viscosity of these compounds is low, and therefore, these compounds are unlikely to increase the viscosity of the composition (X). Furthermore, since these compounds hardly volatilize, the storage stability of the composition (X) is easily improved.

  It is preferable that the amount of the component (c) is 5% by mass or more and 80% by mass or less based on the whole acrylic compound (A). In this case, the sealing material 5 can achieve both a high glass transition temperature and adhesion to a member made of an inorganic material. The amount of the component (c) is more preferably from 5% by mass to 60% by mass, and particularly preferably from 5% by mass to 50% by mass.

  It is preferable that the acrylic compound (A) does not contain a compound having nitrogen. Therefore, it is preferable that the acrylic compound (A) does not contain any of the above-mentioned morpholine acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. In this case, the viscosity of the composition (X) does not easily increase during storage of the composition (X). This is considered to be because when the composition (X) contains the compound having nitrogen and the moisture absorbent (C), the compound having nitrogen and the moisture absorbent (C) easily react with each other.

  The acrylic compound (A) preferably contains a compound having no polar group other than the (meth) acryloyl group in an amount of 50% by mass or more based on the whole acrylic compound (A). In this case, since the acrylic compound (A) has a good affinity with the dispersant (D), the dispersibility of the moisture absorbent (D) tends to be particularly high. The polar group is, for example, a group containing nitrogen and a group containing oxygen. The compound having no polar group other than the (meth) acryloyl group is, for example, a compound in which the molecular skeleton other than the (meth) acryloyl group is composed of only carbon and hydrogen. The amount of the compound having no polar group other than the (meth) acryloyl group is more preferably 60% by mass or more, and further preferably 80% by mass or more.

  The composition (X) may further contain a radical polymerizable compound (E) other than the acrylic compound (A). The radical polymerizable compound (E) includes a polyfunctional radical polymerizable compound (E1) having two or more radical polymerizable functional groups in one molecule and a monofunctional compound having only one radical polymerizable functional group in one molecule. Any one or both of the radically polymerizable compound (E2) can be contained. The amount of the radical polymerizable compound (E) based on the total amount of the acrylic compound (A) and the radical polymerizable compound (E) is, for example, 10% by mass or less. The polyfunctional radical polymerizable compound (E1) is, for example, a group consisting of an aromatic urethane oligomer, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer and other special oligomers having two or more ethylenic double bonds in one molecule. And at least one compound selected from the group consisting of: The monofunctional radically polymerizable compound (E2) includes, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidylether, butylglycidylether, 2-ethylhexylglycidylether, allylglycidylether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxide decane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam.

  The photo-radical polymerization initiator (B) is not particularly limited as long as it is a compound that generates a radical species when irradiated with ultraviolet rays. Examples of the radical photopolymerization initiator (B) include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole It contains at least one compound selected from the group consisting of compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds. The amount of the photoradical polymerization initiator (B) is, for example, 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the composition (X).

  The composition (X) may contain a polymerization accelerator in addition to the photoradical polymerization initiator (B). Examples of the polymerization accelerator include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl.

  The photo-radical polymerization initiator (B) may contain a sensitizer as a part of the photo-radical polymerization initiator (B). The sensitizer can promote the radical generation reaction of the photoradical polymerization initiator (B), improve the reactivity of the radical polymerization, and increase the crosslink density. The sensitizer is, for example, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, 1,2- Dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, At least one selected from the group consisting of 4,4'-bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde It may contain one compound.

  The content of the sensitizer in the composition (X) is, for example, 0.1 part by mass or more and 5 parts by mass or less, preferably 0.1 part by mass, based on 100 parts by mass of the solid content of the composition (X). To 3 parts by mass. When the content of the sensitizer is in such a range, the composition (X) can be cured in the air, and the composition (X) needs to be cured under an inert atmosphere such as a nitrogen atmosphere. Disappears.

  The composition (X) may contain a polymerization accelerator in addition to the photoradical polymerization initiator (B). Examples of the polymerization accelerator include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl.

  The hygroscopic agent (C) is preferably inorganic particles having hygroscopicity, and for example, contains at least one component selected from the group consisting of zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. Is preferred. It is particularly preferred that the desiccant (C) contains zeolite particles.

  The zeolite particles having an average particle size of 200 nm or less can be produced by, for example, grinding a general industrial zeolite. In producing the zeolite particles, the zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Such a method for producing zeolite particles is disclosed in JP-A-2006-69266, JP-A-2013-049602, and the like.

  The zeolite particles are preferably produced using a zeolite containing sodium ions as a raw material. Among the zeolites containing sodium ions, at least one selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite is used as a raw material. Is more preferable. It is particularly preferable that the zeolite particles be produced using 4A zeolite as a raw material among A zeolite. In these cases, the zeolite particles have a crystal structure suitable for adsorbing moisture.

  One specific example of a method for producing zeolite particles having an average particle size of 200 nm or less will be described. First, a zeolite powder as a raw material is prepared, and this zeolite powder is physically pulverized. For example, the zeolite powder can be physically pulverized by mixing the zeolite powder with water to prepare a slurry and applying the slurry to a bead mill pulverizer.

  Subsequently, the zeolite powder is crystallized by hydrothermal synthesis. For example, hydrothermal synthesis can be performed by heating a slurry containing zeolite powder after physical pulverization in an autoclave. The conditions for the hydrothermal synthesis are, for example, a heating temperature of 150 to 200 ° C. and a heating time of 15 to 24 hours.

  Subsequently, the zeolite powder is dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or the like and then sieved to adjust the particle size.

  Subsequently, if necessary, the zeolite powder is subjected to an ion exchange treatment. In particular, when the zeolite powder is a zeolite containing sodium such as LTA, it is preferable to perform an ion exchange treatment for exchanging sodium in the zeolite powder for magnesium.

  The ion exchange treatment is performed, for example, by dispersing zeolite powder in an aqueous solution containing magnesium ions to prepare a mixture, and heating the mixture. More specifically, the ion exchange treatment is performed, for example, as follows. First, the zeolite powder is mixed with magnesium chloride and water, and the resulting mixture is stirred while being heated. During this treatment, the operation of temporarily stopping the stirring, discarding the supernatant of the mixture, subsequently replenishing the mixture with water, and then restarting the stirring is preferably repeated a plurality of times at appropriate intervals. . The heating temperature in this treatment is preferably in the range of 40 to 80 ° C, and the treatment time is preferably in the range of 6 to 8 hours.

  When the ion exchange treatment is performed, the zeolite powder is subsequently dried. The drying temperature is, for example, in the range of 150 to 200 ° C., and the drying time is, for example, in the range of 2 to 3 hours. Subsequently, if necessary, the dried zeolite powder is crushed using a mortar or the like and then sieved to adjust the particle size. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

Crystallization of the zeolite powder can also be performed in the presence of silicate and alkali metal oxide. A specific example of a method for producing zeolite particles having an average particle size of 200 nm or less in that case will be described. First, a zeolite powder is prepared. Zeolite powder preferably has a composition of _{aM1 2 O · bSiO 2 · Al} 2 O 3 · cMe. M1 is an alkali metal, proton or ammonium ion (NH ₄ ⁺ ), Me is an alkaline earth metal, a is a number in the range of 0.01 to 1, and b is in the range of 20 to 80 And c is a number in the range of 0 to 1. The zeolite powder preferably contains a zeolite containing sodium ions, and contains at least one material selected from the group consisting of A-type zeolites, X-type zeolites and Y-type zeolites among zeolites containing sodium ions. More preferred. It is particularly preferred that the zeolite powder contains 4A zeolite among A zeolite. The zeolite powder is physically pulverized. For example, zeolite powder can be physically pulverized by passing it through a bead mill pulverizer.

The zeolite powder after the physical pulverization is dispersed in a solution containing M2 ₂ O, SiO ₂ and H ₂ O to prepare a slurry. M2 is an alkali metal, preferably K or Na. The molar ratio of M2 ₂ O / H ₂ O is, for example, in the range of 0.003 to 0.01, and the molar ratio of SiO ₂ / H ₂ O is, for example, in the range of 0.006 to 0.025. The amount of the zeolite powder is, for example, 0.5 to 10 g per 100 ml of the solution.

  The zeolite powder can be crystallized by heating the slurry in an autoclave. The conditions are, for example, a heating temperature of 100 to 230 ° C. and a heating time of 1 to 24 hours. Subsequently, the zeolite powder is washed and dried. Thereby, zeolite particles having an average particle size of 200 nm or less can be obtained.

  The pH of the zeolite particles is preferably from 7 to 10. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are less likely to be broken, so that the sealing material made from the composition (X) containing the zeolite particles can have particularly high hygroscopicity. When the pH of the zeolite particles is 10 or less, the zeolite particles hardly inhibit the curing when the composition (X) is cured.

  The pH of the zeolite particles was determined by heating a dispersion obtained by adding 0.05 g of zeolite particles to 99.95 g of ion-exchanged water at 90 ° C. for 24 hours, and then measuring the pH of the supernatant of the dispersion with a pH meter. It is a value obtained by measuring with. As the pH measuring device, for example, a compact pH meter <LAQUATwin> B-711 manufactured by Horiba, Ltd. can be used.

  In order for the pH of the zeolite particles to be 7 or more and 10 or less, it is preferable that the zeolite particles be made of a FAU Y-type zeolite having a proton as a counter cation.

  In the process of producing the zeolite particles, when performing hydrothermal synthesis of zeolite, a treatment for adjusting pH may be performed. The treatment for adjusting the pH is performed, for example, before heating the slurry containing the zeolite powder prepared for hydrothermal synthesis, during heating the slurry, or after heating the slurry. The pH is adjusted by, for example, adding an acid to the slurry. The acid contains at least one component selected from the group consisting of inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid and organic acids such as formic acid, acetic acid and oxalic acid.

  The average particle size of the moisture absorbent (C) is preferably 10 nm or more and 200 nm or less. When the average particle size is 200 nm or less, the cured product can have particularly high transparency. Further, when the average particle size is 10 nm or more, good hygroscopicity of the hygroscopic agent (C) can be maintained. The average particle diameter is a median diameter calculated from the measurement result by the dynamic light scattering method, that is, a cumulative 50% diameter (D50). As a measuring device, a Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

  The average particle size of the hygroscopic agent (C) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. The average particle size of the moisture absorbent (C) is preferably 20 nm or more, more preferably 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

  The 90% cumulative diameter (D90) of the hygroscopic agent (C) is preferably 300 nm or less, and more preferably 100 nm or less. In this case, the cured product can have particularly high transparency.

  The ratio of the moisture absorbent (C) to the total amount of the composition (X) is preferably from 1% by mass to 20% by mass. When the proportion of the hygroscopic agent (C) is 1% by mass or more, the cured product can have particularly high hygroscopicity. When the proportion of the moisture absorbent (C) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity that can be applied by an inkjet method. Can also. The proportion of the moisture absorbent (C) is more preferably 3% by mass or more, particularly preferably 5% by mass or more. Further, the proportion of the moisture absorbent (C) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

  The composition (X) may further contain an inorganic filler other than the hygroscopic agent (C). Particularly, the composition (X) preferably contains nano-sized high refractive index particles. Examples of high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the organic EL light emitting device 1, the efficiency of extracting light that passes through the sealing material 5 and is emitted to the outside can be improved. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, and more preferably in the range of 10 to 20 nm.

  The ratio of the high refractive index particles in the composition (X) is appropriately designed so that the cured product has a desired refractive index. In particular, the high refractive index particles are preferably contained in the composition (X) such that the refractive index of the cured product is in the range of 1.45 or more and less than 1.55. In this case, the light extraction efficiency of the organic EL light emitting device 1 is particularly improved.

  The dispersant (D) is a surfactant that can be adsorbed on the moisture absorbent (C). The dispersant (D) includes an adsorbing group (generally also referred to as an anchor) that can be adsorbed on the particles of the hygroscopic agent (C), and a molecular skeleton attached to the particles of the hygroscopic agent (C) by the adsorbing group adsorbing on the particles of the hygroscopic agent (C) (Generally referred to as a tail). The dispersant (D) includes, for example, an acrylic dispersant having an acrylic molecular tail, a urethane dispersant having a urethane molecular tail, and a polyester dispersant having a polyester molecular chain. The composition contains at least one component selected from the group consisting of the agent and the agent.

  Dispersant (D) may include a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. Polymers include, for example, hydroxyl group-containing carboxylic acid esters, salts of long-chain polyaminoamides and high-molecular-weight acid esters, salts of high-molecular-weight polycarboxylic acids, salts of long-chain polyaminoamides and polar acid esters, and high-molecular-weight unsaturated acid esters , Modified polyurethane, modified polyacrylate, polyetherester type anionic surfactant, salt of naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, polyoxyethylene nonylphenyl ether, polyesterpolyamine, and stearylamine acetate It contains at least one component selected from the group. When the dispersant (D) contains a polymer, the steric hindrance effect that occurs when the polymer is adsorbed on the particles of the moisture absorbent (C) is improved, so that the dispersibility of the moisture absorbent (C) can be improved.

  As described above, the dispersant (D) has two or more adsorptive groups in one molecule. For this reason, the dispersant (D) can satisfactorily disperse the moisture absorbent (C). This is because the molecules of the dispersant (D) have two or more adsorbing groups, so that the adsorbing groups are more likely to come into contact with the particles of the hygroscopic agent (C). This is probably because the molecules of the dispersant (D) tend to adhere. For this reason, even though the cured product of the composition (X) and the sealing material 5 contain the moisture absorbent (C), the transparency of the cured product and the sealing material 5 is not easily reduced by the moisture absorbent (C). . In addition, aggregation of the moisture absorbent (C) during storage of the composition (X) is effectively suppressed, so that the storage stability of the composition (X) is not easily reduced by the moisture absorbent (C). Further, the dispersant (D) hardly inhibits the adhesion between the cured product of the composition (X) and the member made of the inorganic material. This is because the molecules of the dispersant (D) tend to adhere to the particles of the hygroscopic agent (C) as described above, so that the free molecules of the dispersant (D) are contained in the composition (X) and its cured product. It is considered that this is because it is unlikely to occur, and thus adhesion of the molecule is hardly inhibited by free molecules. For this reason, the sealing material 5 can have high adhesion to the glass base material. Further, silicon nitride and silicon oxide may be used as the material of the passivation layer 6 in the organic EL light emitting device 1 in some cases. For this reason, when the passivation layer 6 is made of silicon nitride or silicon oxide, the sealing material 5 can have high adhesion to the passivation layer 6. Further, the dispersant (D) hardly generates outgas from the cured product and the sealing material 5. This is presumably because free molecules of the dispersant (D) are hardly generated as described above, and thus outgassing due to the free molecules is hardly generated.

  The adsorptive group in the dispersant (D) preferably contains at least one group selected from the group consisting of an acidic functional group and a basic functional group. In this case, the dispersant (D) can disperse the moisture absorbent (C) particularly well. The adsorbing group may be protected by a suitable protecting group. When the moisture absorbent (C) contains zeolite particles, the adsorbing group preferably contains at least one group selected from the group consisting of a phosphoric acid group, a carboxyl group and an amino group. In this case, the dispersant (D) can disperse the zeolite particles particularly well. It is more preferable that the adsorptive group contains a phosphate group. Each of the phosphate group, carboxyl group and amino group may be protected with a protecting group.

  When the adsorptive group contains an acidic functional group, the acid value of the dispersant (D) is preferably 200 mgKOH / g or less. In this case, it is unlikely that the dispersant (D) reacts with the acrylic compound (A) in the composition (X) without adsorbing to the particles of the moisture absorbent (C). Therefore, the dispersibility of the moisture absorbent (C) is easily improved. The acid value of the dispersant (D) is more preferably 150 mgKOH / g or less, even more preferably 100 mgKOH / g or less. The acid value of the dispersant (D) is, for example, 10 mgKOH / g or more.

  The dispersant (D) can contain, for example, at least one selected from the group consisting of a double-ended dispersant, a comb-shaped dispersant, a side-chain terminal dispersant, and a hyperbranched dispersant. The double-ended dispersant has a structure in which an adsorbing group is bonded to both ends of the tail. The comb-type dispersant has a structure in which a plurality of adsorbing groups are present in a main chain of a comb-shaped tail having a main chain and a plurality of side chains. The side chain terminal type dispersant has a structure in which an adsorbing group is bonded to an end of a side chain of a tail having a main chain and a plurality of side chains, or further, an adsorbing group is bonded to one or both ends of a main chain. . The hyperbranched dispersant has a structure in which a nucleus having an adsorptive group is covered with a branched tail.

  When the dispersant (D) contains at least one selected from the group consisting of a double-end dispersant, a comb-type dispersant, and a side-chain end dispersant, the dispersant (D) has a viscosity of the composition (X). Is difficult to raise. When the dispersant (D) contains a double-ended dispersant, the dispersant (D) hardly increases the viscosity of the composition (X). This is the case of using a double-ended dispersant, a comb-type dispersant or a side-chain terminal dispersant, particularly when using a side-chain terminal dispersant, compared to the case of using a hyperbranched dispersant. It is considered that one reason is that the tails attached to the particles of the moisture absorbent (C) are hardly entangled with each other. If the dispersant (D) does not easily increase the viscosity of the composition (X), the degree of freedom in selecting components other than the dispersant (D) increases. For example, even if the viscosity of the composition (X) is slightly high, A component capable of improving the function can be added to the composition (X), and the viscosity of the composition (X) can be kept low. For example, when the acrylic compound (A) contains the polyfunctional acrylic compound (A1), the polyfunctional acrylic compound (A1) tends to increase the viscosity of the composition (X) because the polyfunctional acrylic compound (A1) has a relatively high viscosity. When the agent (D) does not easily increase the viscosity of the composition (X), the viscosity of the composition (X) is maintained low even if the composition (X) contains the polyfunctional acrylic compound (A1). Cheap. For this reason, it is easy to obtain the effect of increasing the glass transition temperature of the cured product and improving the cured product and the member made of the inorganic material by the polyfunctional acrylic compound (A1).

  When the dispersant (D) contains at least one selected from the group consisting of a comb-type dispersant, a side-chain terminal dispersant, and a hyperbranched dispersant, the dispersant (D) particularly includes the adsorbent (C). It is easy to disperse, and the adhesion between the cured product of the composition (X) and the member made of an inorganic material is hardly hindered. It is considered that the reason is that the molecules of the dispersant (D) are particularly easily adsorbed to the particles of the hygroscopic agent (C), and therefore, free molecules of the dispersant (D) are hardly generated.

  The viscosity of the dispersant (D) is preferably 50,000 mPa · s or less. In this case, the dispersant (D) does not easily increase the viscosity of the composition (X). The viscosity of the dispersant (D) is more preferably 20,000 mPa · s or less, particularly preferably 10,000 mPa · s or less.

  The boiling point of the dispersant (D) is preferably 200 ° C. or higher. In this case, since the dispersant (D) hardly volatilizes from the composition (X), the storage stability of the composition (X) is further improved.

  The weight average molecular weight of the dispersant (D) is preferably 200,000 or less. In this case, the dispersant (D) tends to have a low viscosity. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 50,000 or less. In this specification, the weight-average molecular weight is a relative weight-average molecular weight in terms of polystyrene obtained from a result of measurement by gel permeation chromatography.

  When the dispersant (D) contains a double-ended dispersant, the double-ended dispersant is, for example, SOLPERSER 41000 (trade name, manufactured by Lubrizol Co., Ltd.) g, amine value 0 mgKOH / g, viscosity 1500 mP · s, boiling point 200 ° C. or more) and Lubrizol product number SOLSPERSE45000 (both terminal type dispersant having a phosphate group as an adsorbing group, acid value 235 mgKOH / g, amine value 0 mgKOH) / G, viscosity 1500 mP · s, boiling point 200 ° C. or more).

  When the dispersant (D) contains a comb-type dispersant, the comb-type dispersant may be, for example, SOLPERSER32000 (comb-type dispersant having an amino group as an adsorptive group, acid value 15 mgKOH / g, amine value) 31 mgKOH / g, viscosity 14000 mP · s, boiling point 200 ° C. or higher, and Lubrizol product number SOLSPERSE36000 (comb-type dispersant having a phosphate group as an adsorptive group, acid value 15 mgKOH / g, amine value 0 mgKOH / g, viscosity 15000 mP) S, boiling point of 200 ° C. or more).

  When the dispersant (D) contains a side chain terminal type dispersant, the side chain terminal type dispersant is, for example, product name Actflow CBB3098 manufactured by Soken Kagaku Co., Ltd. Acid value 98 mg KOH / g, amine value 0 mg KOH / g, viscosity 9000 mPa · s, boiling point 200 ° C. or more) and product name Actflow CB3060 manufactured by Soken Chemical Co., Ltd. (side chain terminal type dispersant having a carboxyl group as an adsorbing group, acid value 60 mg KOH) / G, amine value 0 mgKOH / g, viscosity 1200 mPa · s, boiling point 200 ° C. or more).

  When the dispersant (D) contains a hyperbranched dispersant, the hyperbranched dispersant may be, for example, a product number DISPERBYK-2152 manufactured by BYK Chemie (a hyperbranched dispersant having a phosphate group protected by a protective group as an adsorptive group). A dispersant, an acid value of 0 mg KOH / g, an amine value of 0 mg KOH / g, a viscosity of 20,000 mPa · s, and a boiling point of 200 ° C. or more. In DISPERBYK-2152, the acid value is not measured because the phosphate group is protected by a protecting group.

  The amount of the dispersant (D) relative to the moisture absorbent (C) is preferably 40% by mass or less. In this case, the dispersant (D) hardly inhibits the adhesion between the cured product of the composition (X) and the member made of the inorganic material, and hardly generates outgas. It is considered that this is because free molecules of the dispersant (D) are particularly hard to generate. The amount of the dispersant (D) is more preferably 35% by mass or less, and further preferably 30% by mass or less. It is also preferable that the amount of the dispersant (D) is 5% by mass or more based on the moisture absorbent (C). In this case, the dispersant (D) can disperse the moisture absorbent (C) particularly well. The amount of the dispersant (D) is more preferably 10% by mass or more, and even more preferably 15% by mass or more.

  It is preferable that the composition (X) does not contain a solvent. In this case, when preparing a cured product from the composition (X), there is no need to dry the composition (X) to volatilize the solvent. Further, the storage stability of the composition (X) is further increased.

  The composition (X) can be prepared by mixing the above components. The composition (X) is preferably liquid at 25 ° C.

3. Method for Manufacturing Sealing Material and Method for Manufacturing Organic EL Light-Emitting Device A method for manufacturing the sealing material 5 using the composition (X) and a method for manufacturing the organic EL light-emitting device 1 will be described.

  In the present embodiment, it is preferable to form the sealing material 5 by molding the composition (X) by an inkjet method and then irradiating the composition (X) with ultraviolet rays to cure the composition (X). In the present embodiment, the composition (X) can be applied and molded by an inkjet method.

  In applying the composition (X) by the inkjet method, when the composition (X) has a sufficiently low viscosity at room temperature, for example, when the viscosity at 25 ° C. is 30 mPa · s or less, particularly 15 mPa · s or less. Can be formed by applying the composition (X) by an inkjet method without heating.

  When the composition (X) has a property of being reduced in viscosity by being heated, the composition (X) may be heated and then applied to the composition (X) by an ink-jet method to form the composition. When the viscosity at 40 ° C. of the composition (X) is 30 mPa · s or less, particularly 15 mPa · s or less, the viscosity can be reduced by only slightly heating the composition (X). The composition (X) can be discharged by an inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C or higher and 50 ° C or lower.

  More specifically, for example, first, the support substrate 2 is prepared. A partition is formed on one surface of the support substrate 2 by photolithography using, for example, a photosensitive resin material. Subsequently, a plurality of organic EL elements 4 are provided on one surface of the support substrate 2. The organic EL element 4 can be manufactured by an appropriate method such as an evaporation method and a coating method. In particular, it is preferable to manufacture the organic EL element 4 by a coating method such as an ink jet method. Thus, the element array 9 is formed on the support substrate 2.

  Next, a first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be manufactured by an evaporation method such as a plasma CVD method.

  Next, the composition (X) is formed on the first passivation layer 61 by, for example, an inkjet method to form a coating film. If the inkjet method is applied to both the formation of the organic EL element 4 and the application of the composition (X), the manufacturing efficiency of the organic EL light emitting device 1 can be particularly improved. Subsequently, the coating film is cured by irradiating the coating material with ultraviolet rays to produce the sealing material 5. The thickness of the sealing material 5 is, for example, not less than 5 μm and not more than 50 μm.

  Next, a second passivation layer 62 is provided on the sealing material 5. The second passivation layer 62 can be manufactured by an evaporation method such as a plasma CVD method.

  Next, an ultraviolet curable resin material is provided on one surface of the support substrate 2 so as to cover the second passivation layer 62, and then the transparent substrate 3 is overlaid on the resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

  Next, ultraviolet light is applied to the transparent substrate 3 from the outside. The ultraviolet light passes through the transparent substrate 3 and reaches the ultraviolet-curable resin material. Thereby, the ultraviolet curable resin material is cured, and the second sealing material 52 is manufactured.

1. Preparation of Compositions Compositions of Examples and Comparative Examples were prepared by mixing the components shown in the column of “Composition” in the following table.

The details of the components shown in the table are as follows. The viscosity of each of the following components is a value measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) at a temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ .

(1) Polyfunctional acrylic compound / SR247: Neopentyl glycol diacrylate, a bifunctional acrylic compound, having a glass transition temperature of 117 ° C. and a viscosity of 6 mPa · s, manufactured by Sartomer, part number SR247.
SR268: tetraethylene glycol diacrylate which is a bifunctional acrylic compound, glass transition temperature 23 ° C, viscosity 20 mPa · s, manufactured by Sartomer, product number SR268.
A-BPE-10: ethoxylated bisphenol A diacrylate which is a bifunctional acrylic compound, glass transition temperature -12 ° C, viscosity 550 mPa · s, manufactured by Shin-Nakamura Chemical Co., Ltd., product number A-BPE-10.
SR351S: trimethylolpropane triacrylate, a trifunctional acrylic compound, having a glass transition temperature of 62 ° C and a viscosity of 106 mPa · s, manufactured by Sartomer.

(2) Monofunctional acrylic compound IBXA: isobornyl acrylate, glass transition temperature 97 ° C, viscosity 8 mPa · s, manufactured by Osaka Organic Chemical Company.
FA-513AS: dicyclopentanyl (meth) acrylate, glass transition temperature 120, viscosity 13 mPa · s, manufactured by Hitachi Chemical Co., Ltd., product number FA-513AS.

(3) Photopolymerization initiator Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF, trade name Irgacure 184.
-IrgacureTPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name IrgacureTPO.

(4) Hygroscopic agent (4-1) Zeolite particles 1
The zeolite particles 1 are manufactured by the following method, and have a D50 of 60 nm, a D90 of 110 nm, and a pH of 10.

  As a starting material zeolite powder, sodium 4A type zeolite having an average particle size of 5 μm was prepared, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized with a bead mill using zirconia beads, and the slurry was left at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed in a mortar, and then passed through a mesh to adjust the particle size, thereby obtaining zeolite particles 1.

  The pH of the zeolite particles was measured by the following method. After placing 0.05 g of zeolite particles and 99.95 g of ion-exchanged water in a polyethylene bottle, the bottle was placed in a thermostat and heated at 90 ° C. for 24 hours. Subsequently, the pH of the supernatant of the liquid in the bottle was measured using a compact pH meter <LAQUAAtwin> B-711 manufactured by Horiba, Ltd.

(4-2) Zeolite particles 2
The zeolite particles 2 are manufactured by the following method, and have a D50 of 150 nm, a D90 of 250 nm, and a pH of 10.

  As a starting material zeolite powder, sodium 4A type zeolite having an average particle size of 5 μm was prepared, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry. The zeolite powder in this slurry was pulverized by a method similar to that for zeolite particles 1 so that the average particle size became 150 nm.

  Subsequently, the slurry was left at a temperature of 180 ° C. for 2 to 3 hours to obtain finely pulverized zeolite powder. This zeolite powder was crushed in a mortar, and then passed through a mesh to adjust the particle size, whereby zeolite particles 2 were obtained.

(4-3) Zeolite particles 3
The zeolite particles 3 are Tosoh product No. zeoram 4A, 100 mesh pass product, which is a powder product not subjected to surface treatment, and has a D50 of 13 μm, a D90 of 30 μm, and a pH of 10.

(5) Dispersant CBB3098: Side chain terminal type dispersant having a carboxyl group as an adsorptive group, acid value 98 mgKOH / g, viscosity 9000 mP · s, weight average molecular weight 3000, manufactured by Soken Chemical, product number CBB3098.
-SOLSPERSE41000: A liquid both-end type dispersant having a phosphate group as an adsorptive group, an acid value of 50 mgKOH / g, a viscosity of 1500 mP · s, a weight average molecular weight of 47000, manufactured by Lubrizol Co., Ltd., product number SOLSPERSE41000.
SOLSPERSE 32000: a wax-like comb-type dispersant having an amino group and a phosphoric acid group as an adsorptive group, an amine value of 31 mgKOH / g, an acid value of 15 mgKOH / g, a viscosity of 14,000 mP · s, a weight average molecular weight of 3900, manufactured by Lubrizol Corporation, Part number SOLSPERSE32000.
-SOLSPERSE36000: Wax-like comb type dispersing agent having a phosphate group as an adsorptive group, acid value 45 mgKOH / g, viscosity 15000 mP · s, weight average molecular weight 4100, manufactured by Lubrizol Co., Ltd., product number SOLSPERSE36000.
DISPERBYK-2152: a hyperbranched dispersant having a phosphate group protected by a protecting group as an adsorptive group, an acid value of 0 mgKOH / g, a viscosity of 20,000 mP · s, a weight average molecular weight of 20,000, and a product number DISPERBYK-2152 manufactured by BYK Chemie.
DISPERBYK-111: a liquid one-end type adsorbent having a phosphate group as an adsorptive group, acid value 129 mgKOH / g, viscosity 900 mP · s.

2. Evaluation Test The following evaluation tests were performed on the examples and comparative examples. The results are shown in the table.

(1) Viscosity The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 25 ° C. and a shear rate of 1000 s ⁻¹ .

(2) Transmittance The composition was applied to form a coating film, and the coating film was formed using an LED-UV irradiator (having a peak wavelength of 365 nm) manufactured by Panasonic Electric Works under the conditions of about 30 mW / cm ² . A film having a thickness of 10 μm was prepared by irradiating with ultraviolet light for 20 seconds and photo-curing. The total light transmittance of this film according to JIS K7361-1 was measured.

(3) Outgas evaluation Outgas when a cured product of the composition was heated was sampled by a headspace method and measured by gas chromatography. 100 mg of the composition was placed in a vial for headspace, and the composition was irradiated with ultraviolet rays using an LED-UV irradiator (peak wavelength: 365 nm) manufactured by Panasonic Electric Works Co., Ltd. under the conditions of an integrated light amount of 1500 mJ / cm ² . After curing, the vial was sealed and heated at 80 ° C. for 30 minutes, and then the gas phase in the vial was introduced into a gas chromatograph for analysis. As a result, the case where the generated gas was 300 ppm or less was evaluated as “A”, the case where it was more than 300 ppm and less than 500 ppm was evaluated as “B”, and the case where the generated gas was 500 ppm or more was evaluated as “C”.

(4) Ink jetting property The composition is put in a cartridge of an ink jet printer (manufactured by Seiko Epson Corporation, model PX-B700), and after confirming that the composition in the cartridge can be discharged from a nozzle in the ink jet printer, The composition was ejected to continuously print a test pattern. As a result, "A" indicates that the composition could be ejected for one hour and the ejection operation was stable, "B" indicates that the composition could be ejected for one hour but the ejection operation was intermittently unstable, One hour before the start of the discharge, the nozzle was clogged and the composition could not be discharged.

(5) Adhesion The composition was applied to the surface of a quartz glass piece (size: 76 mm × 52 mm × 1 mm) to form a 50 μm-thick coating film, and another quartz glass piece (size: 76 mm) was formed on this coating film. × 52 mm × 1 mm). Subsequently, the coating film was cured by irradiating ultraviolet rays for 20 seconds at about 30 mW / cm ² using an LED-UV irradiator (having a peak wavelength of 365 nm) manufactured by Panasonic Electric Works, Ltd. Next, the adhesion strength between the two quartz glass pieces was evaluated by performing a T-peel test based on JIS K6854.

(6) Storage stability The composition was left under a nitrogen atmosphere at a temperature of 40 ° C for one month. The viscosity of the composition before the test and the viscosity of the composition after the test were measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) at a temperature of 25 ° C. and a shear rate of 1000 s ^−1. And the rate of change in viscosity was calculated from the results. The case where this rate of change was less than 5% was evaluated as "A", the case where it was 5% or more and less than 10% was evaluated as "B", and the case where it was 10% or more was evaluated as "C".

Claims (11)

Acrylic compound (A),
Photopolymerization initiator (B),
It contains a moisture absorbent (C) having an average particle size of 200 nm or less, and a dispersant (D) having two or more adsorption groups in one molecule.
UV curable resin composition. The viscosity at 25 ° C. is 30 mPa · s or less,
The ultraviolet-curable resin composition according to claim 1. The viscosity of the dispersant (D) is 50,000 mPa · s or less,
The ultraviolet curable resin composition according to claim 1. The amount of the dispersant (D) with respect to the moisture absorbent (C) is 40% by mass or less.
The ultraviolet-curable resin composition according to any one of claims 1 to 3. The adsorptive group includes at least one group selected from the group consisting of an acidic functional group and a basic functional group,
The ultraviolet-curable resin composition according to claim 1. The light transmittance of the cured product is 90% or more;
The ultraviolet curable resin composition according to any one of claims 1 to 5. For organic EL element sealing,
The ultraviolet-curable resin composition according to any one of claims 1 to 6. Molded by the inkjet method,
The ultraviolet-curable resin composition according to claim 1. A method for manufacturing an organic EL light emitting device including an organic EL element and a sealing material covering the organic EL element,
The ultraviolet-curable resin composition according to any one of claims 1 to 8 is molded by an ink-jet method, and then the ultraviolet-curable resin composition is irradiated with ultraviolet rays to cure the sealing material. Including making
A method for manufacturing an organic EL light emitting device. After heating the ultraviolet-curable resin composition, the ultraviolet-curable resin composition is molded by an inkjet method,
A method for manufacturing an organic EL light emitting device according to claim 9. An organic EL element and a sealing material covering the organic EL element, wherein the sealing material is a cured product of the ultraviolet-curable resin composition according to any one of claims 1 to 8.
Organic EL light emitting device.