JP2020102430A - Manufacturing method of encapsulating material and manufacturing method of light emitting device - Google Patents

Abstract

To provide a manufacturing method of an encapsulating material and a manufacturing method of a light emitting device, which can enhance the curability of an encapsulating composition at the time of exposure and can efficiently manufacture the encapsulating material.SOLUTION: A manufacturing method of an encapsulating material 5 covering a light emitting element 4 includes a step of irradiating an encapsulating composition of the light emitting element with light after molding the encapsulating composition of the light emitting element in an atmosphere containing oxygen. The encapsulating composition of the light emitting element includes a thiol compound (A), an acrylic compound (B), and a photopolymerization initiator (C).SELECTED DRAWING: Figure 1

Description

The present invention relates to a method of manufacturing a sealing material and a method of manufacturing a light emitting device, and more particularly, to a method of manufacturing a sealing material that covers a light emitting element and a method of manufacturing a light emitting device including the sealing material.

A light emitting device including a light emitting element such as a light emitting diode is applied to lighting applications, display applications, and the like, and is expected to further spread in the future.

When sealing a light emitting element of a light emitting device, for example, an ethylenically unsaturated compound such as an allyl compound and an acrylic compound is mixed with the composition, and the composition is applied and cured so as to cover the light emitting element. By doing so, a sealing material is manufactured.

For example, in Patent Document 1, a (meth)acrylic copolymer (A) obtained by polymerizing a monomer mixture containing a (meth)acrylate macromonomer (a) and a vinyl monomer (b) is used. It discloses a pressure-sensitive adhesive composition containing a photoinitiator, and irradiating the composition with ultraviolet rays to cure the composition to seal the organic EL device.

JP, 2016-222840, A

However, in Patent Document 1, when the composition is cured, if the exposure is performed in an atmosphere containing oxygen, the curability of the composition decreases during the polymerization reaction, and there is a problem that the semiconductor element cannot be sufficiently sealed. .. Therefore, it is necessary to perform the exposure under an atmosphere of an inert gas such as nitrogen, and when manufacturing the encapsulating material, the manufacturing process such as filling the inert gas and maintaining the airtightness of the atmosphere becomes complicated. There was also.

An object of the present invention is to provide a method for manufacturing a sealing material and a method for manufacturing a light emitting device, which can enhance the curability of a sealing composition during exposure and can efficiently manufacture a sealing material. is there.

A method for producing a sealing material according to an aspect of the present invention is a method for producing a sealing material that covers a light emitting element, which comprises molding a composition for sealing a light emitting element, and then under an atmosphere containing oxygen, Irradiating the composition for sealing a light emitting device with light. The light emitting element encapsulating composition contains a thiol compound (A), an acrylic compound (B), and a photopolymerization initiator (C).

A method for manufacturing a light emitting device according to one aspect of the present invention is a method for manufacturing a light emitting device that includes a light emitting element and a sealing material that covers the light emitting element. Producing the encapsulant by the method for producing the encapsulant.

One aspect of the present invention has an advantage that the curability of the encapsulating composition at the time of exposure can be enhanced, and an encapsulating material and a light emitting device including the encapsulating material can be efficiently obtained.

It is a schematic sectional drawing which shows the 1st example of the light-emitting device in one Embodiment of this invention. It is a schematic sectional drawing which shows the 2nd example of the light-emitting device in one embodiment of this invention.

1. Light Emitting Element Encapsulating Composition First, a light emitting element encapsulating composition for producing an encapsulating material will be described.

The light emitting element sealing composition according to this embodiment (hereinafter, also referred to as composition (X)) comprises a thiol compound (A) having two or more thiol groups in one molecule, an acrylic compound (B), And a polymerization initiator (C). In the present embodiment, after molding the composition (X), the composition (X) is irradiated with light in an atmosphere containing oxygen, whereby a sealing material that covers the light emitting element can be manufactured. Since the composition (X) contains the thiol compound (A), oxygen inhibition is easily suppressed in polymerizing the composition (X) even in an atmosphere containing oxygen. Therefore, the composition (X) can be cured well. Furthermore, in the present embodiment, as described above, since the composition (X) can be cured in an atmosphere containing oxygen, an inert gas such as nitrogen is used when the composition (X) is cured to obtain a cured product. It is possible to reduce the number of manufacturing steps such as filling an environment with an inert gas atmosphere during polymerization or filling an inert gas atmosphere to maintain hermeticity. Therefore, in this embodiment, the sealing material can be efficiently manufactured.

Further, when the composition (X) is cured, even in an atmosphere containing oxygen, it is possible to prevent unreacted components from remaining in the cured product and to prevent byproducts from remaining. Therefore, even if a sealing material is produced from the cured product of the composition (X), it is possible to prevent outgas from being easily generated from the sealing material.

High curability of the composition (X) and suppression of outgas generation can be realized by the composition of the composition (X) described in detail below.

The viscosity of the composition (X) at 25° C. is preferably 1 mPa·s or more and 30 mPa·s or less. In this case, the composition (X) can be applied at a normal temperature by a casting method, an inkjet method or the like to be molded. In particular, when the viscosity is 30 mPa·s or less, when the composition (X) is applied by the inkjet method, the ejection speed of the composition (X) from the nozzle is less likely to decrease. The viscosity is more preferably 20 mPa·s or less, further 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 of the composition (X) at 40° C. is 1 mPa·s or more and 30 mPa·s or less. 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 molded by a method such as a casting method, and the composition (X) can be molded by an inkjet method. Moreover, since the composition (X) can be made to have a low viscosity without being heated significantly, the composition (X) is less likely to change its composition due to the volatilization of the components in the composition (X). The viscosity is more preferably 20 mPa·s or less, further preferably 15 mPa·s or less. It is also preferable that this viscosity is 5 mPa·s or more.

The low viscosity of such composition (X) at 25° C. or 40° C. can also 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 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 components contained in the composition (X) will be described in more detail.

First, the thiol compound (A) will be described.

The composition (X) contains the thiol compound (A) as described above. The thiol compound (A) has one or more thiol groups in one molecule. Specifically, the thiol compound (A) is selected from the group consisting of a compound having only one thiol group in one molecule and a polythiol compound (A1) having two or more thiol groups in one molecule. At least one compound. The thiol compound (A) can prevent oxygen inhibition during the curing reaction of the composition (X). Therefore, the thiol compound (A) can easily cure the composition (X) in an oxygen-containing atmosphere such as an air atmosphere. The oxygen inhibition will be described later.

The viscosity of the thiol compound (A) at 25° C. is preferably 2000 mPa·s or less. In this case, the thiol compound (A) is unlikely to increase the viscosity of the composition (X). Therefore, the thiol compound (A) can contribute to improving the storage stability of the composition (X). Therefore, the composition (X) can be easily molded by an inkjet method without adjusting the viscosity with a solvent. The viscosity of the thiol compound (A) at 25° C. is more preferably 1800 mPa·s or less, further preferably 1500 mPa·s or less. The lower limit of the viscosity of the thiol compound (A) at 25°C is not particularly limited, but is, for example, 20 mPa or more. The viscosity in this specification is measured with a rheometer at a shear rate of 1000 s ^-1 . As the rheometer, for example, model number DHR-2 manufactured by Anton Paar Japan can be used.

The thiol compound (A) preferably contains a polythiol compound (A1) having two or more thiol groups in one molecule. In this case, the polythiol compound (A1) can make the curing reaction less likely to occur in the composition (X) during storage of the composition (X), and thus can further improve the storage stability of the composition (X). ..

The number of thiol groups in one molecule of the polythiol compound (A1) is not particularly limited as long as it is 2 or more. For example, the polythiol compound (A1) is a bifunctional thiol compound (A11) having two thiol groups in one molecule, a trifunctional thiol compound (A12) having three thiol groups in one molecule, and At least one compound selected from the group consisting of tetrafunctional thiol compounds (A13) having four thiol groups can be contained. Of course, the polythiol compound (A1) may contain a compound having 5 or more thiol groups in one molecule.

The thiol group of the thiol compound (A) may contain any of a primary thiol group, a secondary thiol group, and a tertiary thiol group. When the thiol compound (A) has, for example, two thiol groups, more specifically, when the thiol compound (A) contains the bifunctional thiol compound (A11), the bifunctional thiol compound (A11) is It may contain a compound having a primary thiol group, may contain a compound having one primary thiol group and one secondary thiol group, and may contain a compound having two secondary thiol groups. It may contain a compound having one secondary thiol group and one tertiary thiol group, or may contain a compound having two tertiary thiol groups. The thiol compound (A) preferably contains a compound having two or more secondary thiol groups. In this case, the thiol compound (A) can make it more difficult to increase the viscosity of the composition (X). This is because, in a compound having two or more secondary thiol groups, the steric hindrance around the thiol group becomes large, so that the thiol compound (A) becomes particularly difficult to react during storage of the composition (X). It is presumed that

As described above, the thiol compound (A) can hardly cause oxygen inhibition during the curing reaction of the composition (X). In the present embodiment, the term “oxygen inhibition” means that the presence of oxygen in the polymerization reaction system of the acrylic compound (B) inhibits the polymerization reaction of the acrylic compound (B). It is considered that the reason why the thiol compound (A) can hardly cause oxygen inhibition is that an ene-thiol reaction occurs with the acrylic compound (B) and the thiol compound (A) during the curing reaction of the composition (X). To be Specifically, when oxygen is present during the polymerization reaction of the acrylic compound (B), radical species derived from the acrylic compound (B) during the polymerization may react with oxygen to generate a peroxide. The generated peroxide can usually terminate the polymerization reaction by undergoing a coupling reaction between the peroxides or by reacting with a growing radical in the polymerization reaction. In this case, it is difficult to satisfactorily advance the polymerization reaction of the acrylic compound (B) in the composition and sufficiently cure it. Here, the thiol compound (A) reacts with the peroxide of the acrylic compound (B) generated by the reaction with oxygen to generate a thiyl radical derived from the thiol compound (A), and the composition (X) The radical species for promoting the growth reaction in the polymerization reaction can be regenerated. Further, the thiol compound (A) can also generate a thiyl radical by reacting with the photopolymerization initiator (C). Therefore, the thiol compound (A) can suppress the deactivation of radical species necessary for the polymerization reaction in the polymerization reaction of the composition (X) even in the presence of oxygen, and thus the reaction of the composition (X). Is considered to be less likely to be hindered. As described above, the composition (X) is easily cured even in an atmosphere containing oxygen such as an air atmosphere. Therefore, in producing a cured product from the composition (X), the cured product of the composition (X) can be efficiently produced even under conditions such as an atmosphere of an inert gas such as nitrogen and conditions under which hermeticity is ensured. Easy to make. Therefore, in manufacturing a cured product from the composition (X), a sealing material made of the cured material, and a light emitting device including the sealing material, it is possible to reduce manufacturing cost and manufacturing man-hours. Can also contribute. The atmosphere containing oxygen is, for example, an atmosphere having an oxygen concentration of 150 L/m ³ or more. Of course, the component contained in the atmosphere containing oxygen is not limited to oxygen and may further contain, for example, an inert gas.

The thiol compound (A) is selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(mercaptopropionate), and the like. It contains at least one compound. The components that can be contained in the thiol compound (A) are not limited to the above.

The content of the thiol compound (A) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is preferably 0.5% by mass or more and 10% by mass or less. When the content of the thiol compound (A) is 0.5% by mass or more, the viscosity of the composition (X) can be further reduced, and the storage stability of the composition (X) can be easily obtained. Moreover, when the content of the thiol compound (A) is 10% by mass or less, the curability of the composition (X) can be further improved. Moreover, when it is in this range, it is particularly easy to mold the composition (X) by an inkjet method. The content of the thiol compound (A) is more preferably 1% by mass or more and 8% by mass or less, and further preferably 2% by mass or more and 6% by mass or less.

The composition (X) contains the acrylic compound (B) as described above.

The viscosity of the entire acrylic compound (B) at 25° C. is preferably 50 mPa·s or less. In this case, the acrylic compound (B) can contribute to lowering the viscosity of the composition (X). The viscosity of the entire acrylic compound (B) is more preferably 30 mPa·s or less, further preferably 20 mPa·s or less. The viscosity of the entire acrylic compound (B) is, for example, 3 mPa·s or more.

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

The compound that the acrylic compound (B) may contain will be described.

The acrylic compound (B) has one or more (meth)acryloyl groups in one molecule. That is, the acrylic compound (B) comprises a polyfunctional (meth)acrylic compound (B10) having two or more (meth)acryloyl groups in one molecule and only one (meth)acryloyl group in one molecule. And a monofunctional (meth)acrylic compound (B20) having. In addition, "(meth)acry" means at least one of "acry" and "methacry". In addition, in the acrylic compound (B), a compound having one or more acryloyl groups in one molecule is referred to as a compound (B1), and a compound having one or more methacryloyl groups in one molecule is also referred to as a compound (B2). .. The compound (B1) and the compound (B2) may be included in either the polyfunctional (meth)acrylic compound (B10) or the monofunctional (meth)acrylic compound (B20).

The acrylic compound (B) preferably contains the compound (B1) and the compound (B2), and the mass ratio of the compound (B1) to the compound (B2) is preferably 1 or more. In this case, when the composition (X) is cured, the curability of the composition (X) can be further improved.

The acrylic compound (B) preferably contains a polyfunctional (meth)acrylic compound (B10). In this case, the polyfunctional (meth)acrylic compound (B10) can increase the glass transition temperature of the cured product of the composition (X), and thus the heat resistance of the cured product. The amount of the polyfunctional (meth)acrylic compound (B10) is, for example, 50% by mass or more and 100% by mass or less based on the entire acrylic compound (B). The acrylic compound (B) may contain only the polyfunctional (meth)acrylic compound (B10).

The polyfunctional (meth)acrylic compound (B10) is, for example, 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, cyclohexanedimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, penta Triestol tetraacrylate, 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, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, hydroxypivalin Acid neopentyl glycol diacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, tetra Methylol propane Triacrylate, tetramethylolmethane triacrylate, caprolactone modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, Dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di It contains at least one compound selected from the group consisting of (meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.

The acrylic equivalent of the polyfunctional (meth)acrylic compound (B10) 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 (meth)acrylic compound (B10) is, for example, 100 or more and 1000 or less, and more preferably 200 or more and 800 or less.

The polyfunctional (meth)acrylic compound (B10) may include 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, the shrinkage when the composition (X) is cured can be particularly reduced. Furthermore, the adhesion between the cured product and the member made of an inorganic material can be enhanced. The polyfunctional (meth)acrylic compound (B10) is selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentatriestol tetraacrylate. It may contain at least one kind of compound. These compounds can particularly reduce shrinkage when the composition (X) is cured. Furthermore, these compounds can also improve the adhesiveness between a cured product and a member made of an inorganic material.

The polyfunctional (meth)acrylic compound (B10) particularly preferably contains the compound (B101) having a structure represented by the following formula (1).

^{_{CH 2 = CR 1 -COO- (R}} 3 -O) n -CO-CR 2 = CH 2 ... (1)
In the formula (1), each of R ¹ and R ² is hydrogen or a methyl group, n is an integer of 1 or more, R ³ is an alkylene group having 3 or more carbon atoms, and when n is 2 or more, A plurality of R ³ may be the same or different from each other.

The compound (B101) has a structure represented by the formula (1), and in particular, when R ³ of the formula (1) has 3 or more carbon atoms, it is difficult to enhance the affinity of the sealing material 5 with water. Therefore, the light emitting element 4 is less likely to be deteriorated by water. The carbon number of R ³ is, for example, 3 or more and 15 or less. Further, the compound (B101) has a structure represented by the formula (1), and particularly has two (meth)acryloyl groups in one molecule, whereby the glass transition temperature of the cured product can be increased. The heat resistance of the cured product can be increased. Further, n in the formula (1) is, for example, an integer of 1 or more and 12 or less.

The percentage of the compound (B101) to the acrylic compound (B) is preferably 50% by mass or more. In this case, it is difficult to increase the affinity of the cured product for water. The percentage ratio of the compound (B101) to the acrylic compound (B) is, for example, 100% by mass or less, or 95% by mass or less, and preferably 80% by mass or less.

The compound (B101) particularly preferably contains the compound (B102) having a boiling point of 270° C. or higher. That is, the acrylic compound (B) preferably contains the compound (B102) having the structure represented by the formula (1) and having a boiling point of 270° C. or higher. In this case, the acrylic compound (B) is less likely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Further, even if the compound (B102) remains unreacted in the cured product of the composition (X), outgas caused by the compound (B102) is unlikely to be generated from the cured product. Therefore, voids due to outgas are unlikely to occur in the light emitting device 1. If there is a void in the light emitting device 1, water may enter the light emitting element 4 through the void. However, if the void is unlikely to occur, water does not easily enter the light emitting element 4. The boiling point is a boiling point under normal pressure, which is obtained by converting the boiling point under reduced pressure, and is determined by the method shown in Science of Petroleum, Vol. II. P. 1281 (1938), for example. The boiling point of the compound (B102) is more preferably 280°C or higher.

The percentage of the compound (B102) to the acrylic compound (B) is preferably 50% by mass or more. In this case, the storage stability of the composition (X) is effectively increased, the outgas generation from the encapsulating material 5 is effectively reduced, and further, the affinity of the encapsulating material 5 for water is hardly increased. .. The percentage of the compound (B102) with respect to the acrylic compound (B) is, for example, 100% by mass or less, or 95% by mass or less, and preferably 80% by mass or less.

The viscosity of the compound (B102) at 25° C. is preferably 25 mPa·s or less. In this case, the compound (B102) can reduce the viscosity of the composition (X). The viscosity of the compound (B102) at 25° C. is more preferably 25 mPa·s or less, further preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity of the compound (B102) at 25° C. is, for example, 1 mPa·s or more, preferably 3 mPa·s or more, and more preferably 5 mPa·s or more.

The compound (B102) is, for example, a group consisting of di(meth)acrylic acid ester of alkylene glycol, di(meth)acrylic acid ester of polyalkylene glycol, and di(meth)acrylic acid ester of alkylene oxide-modified alkylene glycol. It contains at least one compound selected from

The di(meth)acrylic acid ester of alkylene glycol is a compound in which n is 1 in the formula (1). In this case, the carbon number of R ³ in the formula (1) is preferably 4-12. R ³ may be linear or may have a branch. Particularly, di(meth)acrylic acid ester of alkylene glycol includes 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, and 1,9- Nonanediol diacrylate, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9 -It is preferable to contain at least one compound selected from the group consisting of nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate. The di(meth)acrylic acid ester of alkylene glycol is a product number SR213 manufactured by Sartomer, a product number V195 manufactured by Osaka Organic Chemical Industry, a product number SR212 manufactured by Sartomer, a product number SR247 manufactured by Sartomer, and Kyoei Chemical Industry Co., Ltd. Product name Light acrylate NP-A, Sartomer product number SR238NS, Osaka Organic Chemical Industry product number V230, Daicel product number HDDA, Kyoei Chemical Industry product number 1,6HX-A, Osaka Organic Chemical Industry Co., Ltd. Product number V260 manufactured by Kyoei Chemical Industry Co., Ltd., product number 1,9-ND-A manufactured by Kyoei Chemical Industry Co., Ltd. Product number A-NOD-A manufactured by Shin Nakamura Chemical Co., Ltd. Product number CD595 manufactured by Sartomer Company, product number SR214NS manufactured by Sartomer Company, Shin Nakamura Chemical industry product number BD, Sartomer product number SR297, Sartomer product number SR248, Kyoei Chemical Industry product name light ester NP, Sartomer product number SR239NS, Kyoei chemical product product light ester 1 , 6HX, product number HD-N manufactured by Shin-Nakamura Chemical Co., Ltd., product name Light Ester 1,9ND manufactured by Kyoei Chemical Industry Co., Ltd. product number NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd. product name Light Ester 1 manufactured by Kyoei Chemical Co., Ltd. , 10DC, product number DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., and product number SR262 manufactured by Sartomer Co., Ltd. are preferably contained.

The di(meth)acrylic acid ester of polyalkylene glycol is a compound in which n is 2 or more in the formula (1). n is, for example, 2 to 10, preferably 2 to 7, preferably 2 to 6, and more preferably 2 to 3. The carbon number of R ³ is, for example, 2 to 5. The higher the carbon number, the higher the hydrophobicity of the cured product, and the sealing material 5 is less likely to allow moisture to permeate. The di(meth)acrylic acid ester of polyalkylene glycol includes diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol dimethacrylate. It is preferable to contain at least one compound selected from the group consisting of acrylate, tripropylene glycol dimethacrylate and tritetramethylene glycol diacrylate. In addition, the di(meth)acrylic acid ester of polyalkylene glycol is a product number SR230 manufactured by Sartomer, a product number SR508NS manufactured by Sartomer, a product number DPGDA manufactured by Daicel, a product number SR306NS manufactured by Sartomer, and a product number TPGDA manufactured by Dicel. , Osaka Organic Chemical Industry Co., Ltd. product number V310HP, Shin Nakamura Chemical Co., Ltd. product number APG200, Kyoei Chemical Industry Co., Ltd. product name light acrylate PTMGA-250, Sartomer company product number SR231NS, Kyoei Chemical Co., Ltd. product name light Ester 2EG, product number SR205NS manufactured by Sartomer, product name light ester 3EG manufactured by Kyoei Chemical Industry, product number SR210NS manufactured by Sartomer, product light ester 4EG manufactured by Kyoei Chemical Industry, product name Acryester HX manufactured by Mitsubishi Chemical and new It is preferable to contain at least one compound selected from the group consisting of product number 3PG manufactured by Nakamura Chemical Co., Ltd.

The di(meth)acrylic acid ester of alkylene oxide-modified alkylene glycol contains, for example, propylene oxide-modified neopentyl glycol. The di(meth)acrylic acid ester of alkylene oxide-modified alkylene glycol contains, for example, product number EBECRYL145 manufactured by Daicel Corporation.

The percentage of the components having a boiling point of 270° C. or higher in the acrylic compound (B) is preferably 80% by mass or higher. When the acrylic compound (B) contains the compound (B102), the percentage of components including the compound (B102) having a boiling point of 270° C. or higher in the acrylic compound (B) is 80% by mass or more. Is preferred. In this case, the storage stability of the composition (X) is not particularly impaired, and outgas is not easily generated from the cured product. It is more preferable that the percentage of the components having a boiling point of 280° C. or higher in the acrylic compound (B) is 80% by mass or higher.

The compound (B101) may contain a compound (B103) other than the compound (B102).

The polyfunctional (meth)acrylic compound (B10) may contain a compound (B104) having three or more (meth)acryloyl groups in one molecule. That is, the acrylic compound (B) may contain the compound (B104). In this case, the compound (B104) can contain at least one selected from the group consisting of trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, for example. When the acrylic compound (B) contains the compound (B104), the compound (B104) can particularly increase the glass transition temperature of the cured product, and thus can particularly enhance the heat resistance of the cured product.

When the acrylic compound (B) contains the compound (B104), the percentage ratio of the compound (B104) to the acrylic compound (B) is preferably more than 0 mass% and 25 mass% or less. More preferably, the percentage of the compound (B104) is 10% by mass or more. In this case, the glass transition temperature of the cured product can be particularly increased. Further, when the content of the compound (B104) is 25% by mass or less, the viscosity increase of the composition (X) due to the compound (B104) hardly occurs. When the percentage of the compound (B104) is 20% by mass or less, the viscosity increase of the composition (X) is particularly unlikely to occur.

When the acrylic compound (B) contains the compound (B101) having the structure shown in formula (1), it is preferable that the compound (B101) does not contain a compound in which the value of n in formula (1) is 5 or more. .. When (R ³ —O) _n has a polyethylene glycol skeleton, it is particularly preferable not to include a compound in which the value of n in the formula (1) is larger than 5. Even when the compound (B101) includes a compound in which the value of n in the formula (1) is larger than 5, the percentage of the compound in which the value of n in the formula (1) is larger than 5 in the acrylic compound (B) is 20. It is preferably not more than mass %. Further, even when the compound (B101) includes a compound in which the value of n in formula (1) is greater than 5, it is preferable that the compound (B101) does not include a compound in which the value of n is greater than 9. It is even more preferred not to include compounds with values greater than 7. In these cases, the increase in the viscosity of the composition (X) is particularly unlikely to occur.

The acrylic compound (B) can contain a monofunctional (meth)acrylic compound (B20) as described above. The monofunctional (meth)acrylic compound (B20) can suppress shrinkage of the composition (X) during curing. Moreover, the monofunctional (meth)acrylic compound (B20) can contribute to the reduction of the viscosity of the composition (X). When the acrylic compound (B) contains a monofunctional (meth)acrylic compound (B20), the percentage of the monofunctional (meth)acrylic compound (B2) based on the total amount of the acrylic compound (B) is more than 0% by mass and 70% by mass. The following is preferable. When the percentage of the monofunctional (meth)acrylic compound (B20) is more than 0% by mass, the monofunctional (meth)acrylic compound (B20) can suppress the shrinkage of the composition (X) during curing. It is more preferable that the percentage of the monofunctional (meth)acrylic compound (B20) is 5% by mass or more. When the percentage of the monofunctional (meth)acrylic compound (B20) is 70% by mass or less, outgas caused by the monofunctional (meth)acrylic compound (B20) is unlikely to be generated from the composition (X) and the cured product. Further, when the amount of the monofunctional (meth)acrylic compound (B20) is 70% by mass or less, the amount of the polyfunctional component in the acrylic compound (B) can be secured, so that the heat resistance of the cured product can be increased by the polyfunctional component. The property can be particularly improved. The percentage of the monofunctional (meth)acrylic compound (B20) is more preferably 50% by mass or less, further preferably 40% by mass or less of the monofunctional (meth)acrylic compound (B20), and 30% by mass or less. Especially preferred.

Examples of the monofunctional (meth)acrylic compound (B20) include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, and 4-tert-butylcyclohexyl. (Meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, t -Butyl (meth)acrylate, isooctyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxy Ethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydixylethyl (meth)acrylate, ethyldiglycol (meth)acrylate, cyclic trimethylolpropane formal mono (meth)acrylate, imide ( (Meth)acrylate, isoamyl (meth)acrylate, ethoxylated succinic acid (meth)acrylate, trifluoroethyl (meth)acrylate, ω-carboxypolycaprolactone mono(meth)acrylate, cyclohexyl (meth)acrylate, 2-(2-ethoxy) (Ethoxy)ethyl (meth)acrylate, stearyl (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, octyl/decyl (meth)acrylate, tridecyl ( (Meth) acrylate, caprolactone (meth) acrylate, ethoxylated (4) nonylphenol (meth) acrylate, methoxy polyethylene glycol (350) mono (meth) acrylate, methoxy polyethylene glycol (550) mono (meth) acrylate, phenoxyethyl (meth) Acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl ( (Meth)acrylate, tribromophenyl (meth)acrylate, ethoxylated tribromophenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, ethylene oxide adduct of 2-phenoxyethyl (meth)acrylate, acryloylmorpholine, 2- Propylene oxide adduct of phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-methacryloyloxymethylcyclohexene oxide, and 3-(meth)acryloyloxymethylcyclohexene It contains at least one compound selected from the group consisting of oxides.

The monofunctional (meth)acrylic compound (B20) preferably contains a compound having an alicyclic structure. Examples of the compound having an alicyclic structure include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, and diphenyl It contains at least one compound selected from the group consisting of cyclopentenyloxyethyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate and 4-tert-butylcyclohexyl (meth)acrylate.

The monofunctional (meth)acrylic compound (B20) also preferably contains a compound (B201) represented by the following formula (10). In this case, the composition (X) is likely to have a low viscosity, and the sealing material 5 made from the composition (X) is likely to be provided with adhesion to a member made of an inorganic material such as the passivation layer 6. In addition, the compound (B201) has a property of being hard to volatilize despite having a low viscosity. Therefore, even if the composition (X) is stored, the composition (X) is unlikely to change in composition due to volatilization of the monofunctional (meth)acrylic compound (B20).

式（１０）において、Ｒ⁰はＨ又はメチル基である。Ｘは単結合又は二価の炭化水素基である。Ｒ¹からＲ¹¹の各々はＨ、アルキル基又は−Ｒ¹²−ＯＨ、Ｒ¹²はアルキレン基でありかつＲ¹からＲ¹¹のうち少なくとも一つはアルキル基又は−Ｒ¹²−ＯＨである。Ｒ¹からＲ¹¹は互いに化学結合していない。

In formula (10), R ⁰ is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of R ¹ to R ¹¹ is H, an alkyl group or —R ¹² —OH, R ¹² is an alkylene group, and at least one of R ¹ to R ¹¹ 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, the carbon number of X is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. 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, the compound (B201) has an advantage that it has a low 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 or branched. 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-hexyl group or a sec-hexyl group. When the alkyl group is an octyl group, the octyl group may be, for example, a t-octyl group. It is particularly preferable that the alkyl group is a methyl group or a t-butyl group. In this case, the compound (A21) has an advantage that the molecular weight is small and the viscosity is low.

In Formula (10), it is preferable that the alkyl group or -R ¹² -OH is connected only to the 4-position of the cyclohexane ring. That is, it is preferable that, among R ¹ to R ¹¹ , at least one of R ⁶ and R ⁷ is an alkyl group or —R ¹² —OH, and the remaining each is H. It is particularly preferable that, out of R ¹ to R ¹¹ , only R ⁶ is an alkyl group or —R ¹² —OH, and the remaining each is H. In this case, the compound represented by the formula (10) can have good reactivity and is particularly easy to give the sealing material 5 adhesion to the member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (10) has a boat-type conformation, and the bulky alkyl group at the 4-position or —R ¹² —OH is easily located at the pseudo-equatorial position. it is conceivable that. It is considered that the compound represented by the formula (10) having such a structure enhances the reactivity of the (meth)acryloyl group in the compound represented by the formula (10). Further, when the compound represented by the formula (10) has such a structure, the compound represented by the formula (10) can increase the free volume in the sealing material 5. Therefore, it is considered that the interfacial free energy between the sealing material 5 and the inorganic material member is likely to be small, and thus the adhesion between the sealing material 5 and the inorganic material member 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 that the alkyl group or R ¹² has a t-butyl group.

In the formula (10), it is also preferable that an alkyl group or —R ¹² —OH is connected only to each of the 3-position and the 5-position 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, at least one of R ⁸ and R ⁹ is an alkyl group or —R ¹² —OH, and the remaining 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 It is more preferable that each is H. Also in this case, the compound represented by the formula (10) can have good reactivity and is particularly easy to give the sealing material 5 adhesion to a member made of an inorganic material. This is because the cyclohexane ring in the compound represented by the formula (10) has a boat-type conformation, and a bulky alkyl group at each of the 3-position and the 5-position or —R ¹² —OH is located at the pseudo-equatorial position. It is thought that this is because it is easy. For this reason, the reactivity of the (meth)acryloyl group in the compound represented by the formula (10) is increased, as in the case where the alkyl group or -R ¹² -OH is connected only to the 4-position of the cyclohexane ring, and It is considered that the adhesion between the sealing material 5 and the member made of an 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 that the alkyl group or R ¹² has 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, and more preferably 1 or more and 3 or less. R ¹² is, for example, a methylene group, an ethylene group or a propylene group. It is particularly preferable that R ¹² is a methylene group. In this case, the compound (B201) has an advantage that it has a low molecular weight and a low viscosity.

In formula (10), 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 formula (10) can have a particularly low viscosity, and thus the composition (X) can have a particularly low viscosity. Therefore, the composition (X) is particularly easily molded by the inkjet method.

The compound (B201) preferably contains at least one compound selected from the group consisting of the compound represented by the following formula (11), the compound represented by the following formula (12) and the compound represented by the following formula (13).

It is particularly preferable that the monofunctional (meth)acrylic compound (B20) contains at least one of the compound represented by the formula (11) and the compound represented by the formula (12). In this case, the composition (X) is likely to have a particularly low viscosity, the glass transition temperature of the encapsulant 5 is particularly likely to be increased, and the adhesion between the encapsulant 5 and the inorganic material member is particularly easily enhanced. Moreover, since the compound represented by the formula (11) and the compound represented by the formula (12) are less likely to volatilize, the storage stability of the composition (X) is easily improved.

The monofunctional (meth)acrylic compound (B20) also preferably contains a compound having a cyclic ether structure. 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, and 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 monofunctional (meth)acrylic compound (B20) preferably contains at least one compound having a viscosity at 25° C. of 20 mPa·s or less. In this case, the composition (X) may have a low viscosity.

The monofunctional (meth)acrylic compound (B20) preferably contains at least one compound having a glass transition temperature of 80° C. or higher. In this case, the cured product of the composition (X) may have a high glass transition temperature. The monofunctional (meth)acrylic compound (B20) more preferably contains at least one compound having a glass transition temperature of 90° C. or higher, and further preferably contains at least one compound having a glass transition temperature of 100° C. or higher. preferable.

The monofunctional (meth)acrylic compound (B20) preferably contains at least one compound having a boiling point of 200° C. or higher. In this case, the monofunctional (meth)acrylic compound (B20) is unlikely to reduce the storage stability of the composition (X). The monofunctional (meth)acrylic compound (B20) is more preferable if it contains at least one compound having a boiling point of 250° C. or higher.

It is particularly preferable that the monofunctional (meth)acrylic compound (B20) contains at least one compound having a viscosity at 25° C. of 20 mPa·s or less and a glass transition temperature of 80° C. or more. It is also preferable that the monofunctional (meth)acrylic compound (B20) contains at least one compound having a viscosity at 25° C. of 20 mPa·s or less and a boiling point of 200° C. or more. It is also preferable that the monofunctional (meth)acrylic compound (B20) contains at least one compound having a glass transition temperature of 80° C. or higher and a boiling point of 200° C. or higher. The monofunctional (meth)acrylic compound (B20) contains at least one compound having a viscosity at 25° C. of 20 mPa·s or less, a glass transition temperature of 80° C. or more, and a boiling point of 200° C. or more. This is particularly preferable.

Particularly, the monofunctional (meth)acrylic compound (B20) includes isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate and 4-tert-butylcyclohexyl ( It is preferable to contain at least one compound selected from the group consisting of (meth)acrylate. Isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate and 4-tertiarybutylcyclohexyl (meth)acrylate have high glass transition temperature, low viscosity and Since it has a high boiling point, the properties of the composition (X) and the curing agent can be particularly enhanced.

The acrylic compound (B) is selected from the group consisting of a compound having silicon in the molecular skeleton (B41), a compound having phosphorus in the molecular skeleton (B42), and a compound having nitrogen in the molecular skeleton (B43). It is preferable to further contain at least one compound. In this case, the adhesion between the cured material and the sealing material 5 and the member made of an inorganic material such as the passivation layer 6 is improved. Therefore, a gap is unlikely to be formed between the sealing material 5 and the member made of an inorganic material, and water is unlikely to enter the light emitting element 4 through the gap. The acrylic compound (B) particularly preferably contains a compound (B43) having nitrogen in the molecular skeleton (hereinafter, also referred to as a nitrogen-containing acrylic compound (B43)), and the thiol compound (A) and the acrylic compound (B It is preferable that the content of the nitrogen-containing acrylic compound (B43) is 10% by mass or more based on the total amount of (1). In this case, it is possible to improve the adhesiveness between the cured product and the sealing material 5 and the member made of an inorganic material, and further improve the curability of the composition (X) when curing the composition (X). You can The content of the nitrogen-containing acrylic compound (B43) is more preferably 12% by mass or more and 50% by mass or less, and further preferably 15% by mass or more and 35% by mass or less. The compound (B41), the compound (B42) and the nitrogen-containing acrylic compound (B43) are defined by the kinds of atoms in the molecular skeleton. Therefore, a compound included in each of the polyfunctional (meth)acrylic compound (B10) and the monofunctional (meth)acrylic compound (B20) and each of the compound (B41), the compound (B42), and the compound (B43) are included. It may overlap with the compound.

The compound (B41) is, for example, 3-(trimethoxysilyl)propyl acrylate (for example, product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and a (meth)acrylic group-containing alkoxysilane oligomer (for example, product number KR-513 manufactured by Shin-Etsu Chemical Co., Ltd.). ) At least one compound selected from the group consisting of However, since the boiling point of 3-(trimethoxysilyl)propyl acrylate is 260° C., when the acrylic compound (A) contains 3-(trimethoxysilyl)propyl acrylate, the acrylic acid relative to the acrylic compound (A) is The percentage of 3-(trimethoxysilyl)propyl needs to be 10 mass% or less.

The compound (B42) contains acid phosphoxy (meth) acrylate such as acid phosphooxy polyoxypropylene glycol monomethacrylate.

The nitrogen-containing acrylic compound (B43) includes, for example, at least one compound selected from the group consisting of acryloylmorpholine, hydroxyethylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate.

When the acrylic compound (B) contains at least one compound selected from the group consisting of the compound (B41), the compound (B42) and the nitrogen-containing acrylic compound (B43), the compound (B41) for the acrylic compound (B), The percentage of the total amount of the compound (B42) and the nitrogen-containing acrylic compound (B43) is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass or less.

The composition (X) may contain a radically polymerizable compound (G1) other than the acrylic compound (B). The radically polymerizable compound (G1) is a polyfunctional radically polymerizable compound (G11) having two or more radically polymerizable functional groups in one molecule and a monofunctional compound having only one radically polymerizable functional group in one molecule. Either one or both of the radical polymerizable compound (G12) can be contained. The amount of the radical polymerizable compound (G1) with respect to the total amount of the acrylic compound (B) and the radical polymerizable compound (G1) is, for example, 10% by mass or less. The polyfunctional radically polymerizable compound (G11) 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. It may contain at least one compound selected from The components that the polyfunctional radically polymerizable compound (G11) may contain are not limited to the above. The monofunctional radically polymerizable compound (G12) is, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidylether, butylglycidylether, 2-ethylhexylglycidylether, allylglycidylether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, 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 component that the monofunctional radically polymerizable compound (G12) may contain is not limited to the above.

The photopolymerization initiator (C) is not particularly limited as long as it is a compound that generates a radical species when irradiated with light. The photopolymerization initiator (C) includes, for example, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds. , At least one compound selected from the group consisting of a ketoxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, and an alkylamine compound. The amount of the photopolymerization initiator (C) with respect to 100 parts by mass of the composition (X) is, for example, 1 part by mass or more and 10 parts by mass or less. The amount of the photopolymerization initiator (C) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is, for example, 1% by mass or more and 12% by mass or less.

The photopolymerization initiator (C) preferably contains at least one compound selected from the group consisting of an aminoacetophenone compound (C1) and an acylphosphine oxide compound (C2), and the photopolymerization initiator (C) is It is more preferable to contain the aminoacetophenone compound (C1). When the photopolymerization initiator (C) contains the aminoacetophenone compound (C1), the content of the aminoacetophenone compound (C1) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is 1.0 mass. % Or more and 15 mass% or less is preferable. In this case, when the composition (X) is irradiated with light to be cured, the curability of the composition (X) can be further improved. Particularly, when the content of the aminoacetophenone compound (C1) is 1.0% by mass or more, generation of outgas derived from the uncured acrylic compound (B) can be further suppressed. Moreover, when it is 100% by mass or less, the storage stability of the composition (X) can be favorably maintained. The content of the aminoacetophenone compound (C1) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is more preferably 1.5% by mass or more and 10% by mass or less, and 2% by mass or more and 5% by mass or more. The following is more preferable.

Examples of the aminoacetophenone compound (C1) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-benzyl-2-(dimethylamino)-4′. -Morpholinobuchirophenone and the like.

Examples of the acylphosphine oxide (C2) include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

The photopolymerization initiator (C) also preferably contains a sensitizer (D) as a part of the photopolymerization initiator (C). The sensitizer (D) can accelerate the radical formation reaction of the photopolymerization initiator (C), improve the reactivity of radical polymerization, and improve the crosslink density.

The content of the sensitizer (D) in the composition (X) is, for example, 0.1 part by mass or more and 5 parts by mass or less, preferably 0 part by mass, relative to 100 parts by mass of the solid content of the composition (X). It is 1 part by mass or more and 3 parts by mass or less. When the content of the sensitizer is in such a range, the composition (X) can be more easily cured under an atmosphere containing oxygen.

The sensitizer (D) includes, for example, thioxanthone-based sensitizers such as thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; 9,10-dibutoxyanthracene, 9- Anthracene sensitizers such as hydroxymethylanthracene; Anthraquinone sensitizers such as anthraquinone, 1,2-dihydroxyanthraquinone and 2-ethylanthraquinone; 1,4-diethoxynaphthalene; p-dimethylaminoacetophenone, p-diethylaminoacetophenone Acetophenone sensitizers such as; benzophenone sensitizers such as p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone; and At least one compound selected from the group consisting of benzaldehyde sensitizers such as p-dimethylaminobenzaldehyde and p-diethylaminobenzaldehyde can be contained. The sensitizer (D) preferably contains a thioxanthone sensitizer (D1). The content of the thioxanthone sensitizer (D1) with respect to the photopolymerization initiator (C) is preferably 1.0% by mass or more and 90% by mass or less. In this case, the curability of the composition (X) can be further improved. The content of the thioxanthone sensitizer (D1) with respect to the photopolymerization initiator (C) is more preferably 10% by mass or more and 80% by mass or less, and further preferably 20% by mass or more and 70% by mass or less. .. In particular, when the photopolymerization initiator (C) contains the aminoacetophenone compound (C1), the content of the thioxanthone sensitizer (D1) with respect to the aminoacetophenone compound (C1) is 1.0% by mass or more and 100% by mass or more. The following is preferable. In this case, the effect of the sensitizer (D) is particularly remarkable.

The composition (X) may contain a polymerization accelerator in addition to the photopolymerization initiator (C). Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and butoxy p-dimethylaminobenzoate. Contains an amine compound such as ethyl.

The composition (X) may contain a polymerization inhibitor. In particular, when the thiol compound (A) in the composition (X) contains a primary polythiol compound, the storage stability of the composition (X) can be further improved. The content of the polymerization inhibitor with respect to the total amount of the polythiol compound (A) and the acrylic compound (B) is preferably 0.5% by mass or more and 5% by mass or less. Examples of the polymerization inhibitor include at least one compound selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, 1,4-benzoquinone, tert-butylhydroquinone, 4-tert-butylpyrocatechol and the like.

The composition (X) preferably further contains a hygroscopic agent (E). In this case, even if the cured product of the composition (X) is exposed to moisture, the moisture absorbent (E) absorbs the moisture, so that the cured product and the light emitting element 4 in the light emitting device 1 are less likely to deteriorate. The average particle diameter of the hygroscopic agent (E) is preferably 10 nm or more and 200 nm or less. In this case, the cured product can have high transparency.

The hygroscopic agent (E) is preferably inorganic particles having hygroscopicity, and 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. The hygroscopic agent (E) particularly preferably contains zeolite particles.

Zeolite particles having an average particle size of 200 nm or less can be produced, for example, by pulverizing general industrial zeolite. In producing the zeolite particles, the zeolite may be crushed and then crystallized by hydrothermal synthesis or the like. In this case, the zeolite particles can have particularly high hygroscopicity. Examples of the method for producing such zeolite particles are disclosed in JP-A-2016-69266 and JP-A-2013-049602.

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

The average particle diameter of the hygroscopic agent (E) is preferably 10 nm or more and 200 nm or less. When this average particle diameter is 200 nm or less, the cured product can have particularly high transparency. When the average particle size is 10 nm or more, the hygroscopic agent (E) can maintain good hygroscopicity. 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). In addition, as a measuring device, Nanotrack Nanotrac Wave series of Microtrac Bell Co., Ltd. can be used. The average particle diameter of the hygroscopic agent (E) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. Further, the average particle diameter of the hygroscopic agent (E) is preferably 20 nm or more, and more preferably 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

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

When the composition (X) contains the hygroscopic agent (E), the ratio of the hygroscopic agent (E) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. When the proportion of the hygroscopic agent (E) is 1% by mass or more, the cured product can have particularly high hygroscopicity. When the proportion of the hygroscopic agent (E) 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 it can be applied by an inkjet method. Can also The proportion of the hygroscopic agent (E) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Further, the proportion of the hygroscopic agent (E) 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 (E). In particular, 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 of the composition (X) is applied to the sealing material 5 in the light emitting device 1, it is possible to improve the extraction efficiency of light that passes through the sealing material 5 and is emitted to the outside. The average particle diameter of the high refractive index particles is preferably in the range of 5 nm or more and 30 nm or less, and more preferably 10 nm or more and 20 nm or less.

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

The composition (X) may contain a dispersant (F). The dispersant (F) can improve the dispersibility of the components in the composition (X). Therefore, the dispersant (F) can more hardly cause an increase in the viscosity of the composition (X) and a decrease in the storage stability due to the polythiol compound (A). The dispersant (F) is a surfactant that can be adsorbed on the particles. When the composition (X) contains the hygroscopic agent (E), the dispersant (F) can favorably disperse the hygroscopic agent (E). Despite containing the hygroscopic agent (E), the transparency of the cured product and the sealing material 5 is not easily lowered by the hygroscopic agent (E). Further, the dispersant (F) can effectively suppress aggregation of the hygroscopic agent (E) during storage of the composition (X). Therefore, the storage stability of the composition (X) is not easily lowered by the hygroscopic agent (E).

The dispersant (F) has an adsorptive group (generally also referred to as an anchor) that can be adsorbed to the particles, and a molecular skeleton (generally referred to as a tail) that is attached to the particles when the adsorptive group adsorbs to the particles. The dispersant (F) is, for example, an acrylic dispersant whose tail is an acrylic molecular chain, a urethane dispersant whose tail is a urethane molecular chain, and a polyester dispersion whose tail is a polyester molecular chain. The agent contains at least one component selected from the group. The adsorptive group includes, for example, at least one of a basic polar functional group and an acidic polar functional group. The basic polar functional group includes, for example, at least one group selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. The acidic polar functional group includes, for example, at least one group selected from the group consisting of a carboxyl group and a phosphoric acid group. The dispersant (F) is, for example, at least one compound selected from the group consisting of Solsperse series manufactured by Japan Louvre Resor Co., Ltd., DISPERBYK series manufactured by Big Chemie Japan Co., Ltd., and Azisper series manufactured by Ajinomoto Fine-Techno Inc. Can be included.

When the composition (X) contains the hygroscopic agent (E), the amount of the dispersant (F) based on 100 parts by mass of the hygroscopic agent (E) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (F) is 5 parts by mass or more, the function of the dispersant (F) can be effectively exhibited, and when it is 60 parts by mass or less, the cured product (encapsulated product) of the composition (X) It is possible to prevent free molecules of the dispersant (F) in the (stopping material) from inhibiting the adhesion between the sealing material and the member made of an inorganic material. Further, the amount of the dispersant (D) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. preferable.

The dispersant (F) is added to the composition (X) as needed. For example, when the composition (X) does not contain the hygroscopic agent (E), or when the hygroscopic agent (E) does not easily lower the dispersibility, the composition does not need to contain the dispersant. (X) has storage stability.

The composition (X) preferably contains no solvent, or the content of the solvent is 1% by mass or less. In this case, it is not necessary to dry the composition (X) to volatilize the solvent when producing a cured product from the composition (X). Therefore, even if the composition (X) contains the thiol compound (A), outgas is unlikely to be generated from the composition (X) and the cured product. Moreover, the storage stability of the composition (X) is further increased. Then, by producing a sealing material from the composition (X), it is possible to realize that the sealing material 5 contains substantially no solvent. Therefore, in the light emitting device 1, voids due to outgas generated from the sealing material 5 are unlikely to occur. The content of the solvent is more preferably 0.5% by mass or less, further preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferable that the composition (X) does not contain a solvent or contains only a solvent which is inevitably mixed.

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

2. Structure of Light Emitting Device Next, the structure of the light emitting device 1 will be described. The light emitting device 1 includes a light emitting element 4 and a sealing material 5 that covers the light emitting element 4. The sealing material 5 may cover the light emitting element 4 in a state where the sealing material 5 is in direct contact with the light emitting element 4, or may cover the light emitting element 4 in a state in which some layer is interposed between the sealing material 5 and the light emitting element 4. Good. The light emitting device 1 may be, for example, a lighting device or a display device 10 (display).

The light emitting element 4 includes, for example, a light emitting diode. The light emitting diode includes, for example, at least one of an organic EL element (organic light emitting diode) and a micro light emitting diode. When the light emitting element 4 includes an organic light emitting diode, the light emitting device 1 including the light emitting element 4 is, for example, an organic EL display. When the light emitting element 4 includes a micro light emitting diode, the light emitting device 1 including the light emitting element 4 is, for example, a micro LED display. Note that EL means electroluminescence and LED means a light emitting diode.

The encapsulant 5 is preferably a cured product of the light emitting element encapsulating composition described above.

A first example of the structure of the light emitting device 1 will be described with reference to FIG. The light emitting device 1 is a top emission type. The light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap, a light emitting element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and the support substrate 2 and the transparent substrate 3. And a sealing material 5 filled between Further, in the first example, the light emitting device 1 includes the passivation layer 6 that covers the surface of the support substrate 2 facing the transparent substrate 3 and the light emitting element 4. That is, the passivation layer 6 is interposed between the light emitting element 4 and the sealing material 5 that covers the light emitting 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 translucent material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. When the light emitting element 4 includes an organic EL element, the organic EL element 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 injecting layer, a hole transporting layer, an organic light emitting layer, and an electron transporting layer, and these layers are laminated in the order described above. Although only one light emitting element 4 is shown in FIG. 1, even if the light emitting device 1 includes a plurality of light emitting elements 4 and the plurality of light emitting elements 4 form an array on the support substrate 2. Good. The passivation layer 6 is preferably made of silicon nitride or silicon oxide.

A second example of the structure of the light emitting device 1 will be described with reference to FIG. Note that elements common to the first example shown in FIG. 1 are assigned the same reference numerals as those in FIG. 1 in FIG. 2, and detailed description thereof will be omitted as appropriate. The light emitting device 1 shown in FIG. 2 is also a top emission type. The light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap, a light emitting element 4 on a surface of the support substrate 2 facing the transparent substrate 3, and a sealing covering the light emitting element 4. The material 5 is provided.

When the light emitting element 4 includes an organic EL element, the organic EL element includes, for example, a pair of electrodes 41 and 43 and an organic light emitting layer 42 between the electrodes 41 and 43, as in the case of the first example. 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 laminated in the order described above.

The light emitting device 1 includes a plurality of light emitting elements 4, and the plurality of light emitting 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 partition walls 7. The partition wall 7 is on the support substrate 2 and partitions between two adjacent light emitting elements 4. The partition wall 7 is produced, for example, by molding a photosensitive resin material by a photolithography method. The element array 9 also includes connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of the adjacent light emitting elements 4 to each other. The connection wiring 8 is provided on the partition wall 7.

The light emitting device 1 also includes a passivation layer 6 that covers the light emitting element 4. The passivation layer 6 is preferably made of silicon nitride or silicon oxide. The passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the element array 9 while directly contacting the element array 9, thereby covering the light emitting element 4. The second passivation layer 62 is arranged 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 light emitting element 4 and the sealing material 5 that covers the light emitting element 4.

Further, the 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 encapsulating material 5 in the light emitting device 1 having the structure illustrated above can be produced from the light emitting element encapsulating composition according to the present embodiment. That is, the light emitting element sealing composition is used for producing the sealing material 5 for the light emitting element 4. In other words, the light emitting element encapsulating composition is preferably a composition for producing a sealing material, a composition for encapsulating a light emitting element, or a composition for producing a light emitting device.

3. Manufacturing method of sealing material and manufacturing method of light emitting device A manufacturing method of the sealing material 5 and a manufacturing method of the light emitting device 1 using the composition (X) will be described.

In this embodiment, after the composition (X) is molded, the composition (X) is irradiated with light in an atmosphere containing oxygen. The components contained in the composition (X) are as described above. Thereby, the sealing material containing the cured product of the composition (X) can be produced. In the present embodiment, when the composition (X) is irradiated with light, the composition (X) is easily satisfactorily cured even in an atmosphere containing oxygen such as an air atmosphere. Further, outgas is less likely to be generated from the cured product of the composition (X) and the sealing material. Therefore, when manufacturing the encapsulating material 5 from the composition (X), it is possible to reduce the manufacturing cost and the manufacturing man-hours. As described above, the atmosphere containing oxygen is, for example, an atmosphere having an oxygen concentration of 150 L/m ³ or more. Of course, the component contained in the atmosphere containing oxygen is not limited to oxygen and may further contain, for example, an inert gas.

It is preferable to mold the composition (X) by an inkjet method. That is, it is preferable to form the encapsulating material 5 by molding the composition (X) by an inkjet method and then irradiating the composition (X) with light such as ultraviolet rays to cure the composition (X). In this case, foreign matter is unlikely to be mixed in the composition (X) and its cured product, and thus the yield in producing the encapsulating material that covers the light emitting element can be less likely to deteriorate. Thereby, the manufacturing efficiency of the light emitting device 1 including the light emitting element and the sealing material covering the light emitting element can be improved. The composition (X) may be molded in an atmosphere containing oxygen or an atmosphere other than the atmosphere containing oxygen.

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 molded by applying the composition (X) by an inkjet method without heating.

When the composition (X) has a property of lowering the viscosity by being heated, the composition (X) may be heated and then the composition (X) may be applied by an inkjet method to be molded. When the viscosity of the composition (X) at 40° C. is 30 mPa·s or less, particularly 15 mPa·s or less, the composition (X) can be made to have a low viscosity by only slightly heating, and the viscosity can be lowered. 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 wall is formed on one surface of the support substrate 2 by a photolithography method using, for example, a photosensitive resin material. Then, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2. The light emitting element 4 can be manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to manufacture the light emitting element 4 by a coating method such as an inkjet method. As a result, the element array 9 is manufactured on the support substrate 2.

Next, the first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be formed by a vapor deposition 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 light emitting element 4 and the coating of the composition (X), the manufacturing efficiency of the light emitting device 1 can be particularly improved. The composition (X) may be molded by a method other than the inkjet method, for example, a casting method.

Subsequently, the coating film is irradiated with light to be cured, and the sealing material 5 is manufactured. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less. The wavelength of the light with which the coating film is irradiated may be appropriately adjusted depending on the composition of the composition (X), and may be, for example, visible light or ultraviolet light. The wavelength of the light with which the coating film is irradiated is, for example, 385 nm or more. For example, an LED can be used as a light source for emitting light. The wavelength of the irradiation light is preferably 385 nm or more. In this case, when the composition (X) is irradiated with light to be cured, damage to the light emitting element 4 due to the irradiation light can be reduced. Usually, when the wavelength of the irradiation wavelength becomes large, the curability of the resin composition tends to decrease, but since the composition (X) contains the thiol compound (A), a light source having a relatively long wavelength is used. Also has good curability. Thereby, when the sealing material 5 and the light emitting device 1 including the sealing material are produced from the composition (X), the manufacturing efficiency of the light emitting device 1 can be further improved.

The thickness of the sealing material 5 is also preferably 4 μm or more and 50 μm or less, and more preferably 4 μm or more and 15 μm or less. As described above, in the present embodiment, small droplets of the composition (X) are easily formed at a high density by the inkjet method, so that the thin encapsulating material 5 of 4 μm or more and 15 μm or less is easily realized. When the thickness of the sealing material 5 is reduced as described above, tensile stress and compressive stress are less likely to be generated in the sealing material 5 in the light emitting device 1. Therefore, it becomes easy to realize the flexible light emitting device 1.

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

Next, a 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, the transparent substrate 3 is irradiated with light from the outside. The light passes through the transparent substrate 3 and reaches the curable resin material. As a result, the curable resin material is cured and the second sealing material 52 is produced.

Further, as described above, the encapsulating material 5 made of the cured product of the composition (X) can have good heat resistance. Therefore, when the passivation layer 6 (second passivation layer 62) is formed on the sealing material 5 by a vapor deposition method such as a plasma CVD method, the sealing material 5 deteriorates even if the temperature of the sealing material 5 rises. Hard to do. Further, when the light emitting device is used, even if the temperature of the light emitting device 1 rises, the sealing material 5 does not easily deteriorate.

In the above description, the light emitting element encapsulating composition of the present embodiment has been described as being particularly preferably used for producing an encapsulating material for encapsulating a light emitting element. X) can be used to make various objects molded by the inkjet method. Therefore, the use of the composition (X) is not limited to this, and as other uses, a material for a color resist forming a color filter, an interlayer insulating material for insulating between ITO electrodes, a reflection of light of a display device. It may be used to make index matching layers for adjusting index and transmittance. As a specific example, for example, the composition (X) may contain a phosphor, and a color resist in a color filter may be produced from the composition (X). In this case, it is easy to manufacture the color resist in the color filter with high density and high accuracy. This color filter can be provided in a display device such as an organic EL display or a micro LED display.

Hereinafter, specific examples of the present invention will be presented. However, the present invention is not limited to the examples.

1. Preparation of Compositions Compositions of Examples and Comparative Examples were prepared by mixing the components shown in the table below.

The details of the components shown in the table are as follows. Moreover, the viscosity of each of the following components is a value measured using a rheometer (model number DHR-2 manufactured by Anton Paar Japan Co., Ltd.) under the conditions of a temperature of 25° C. and a shear rate of 1000 s ⁻¹ .

(1) Acrylic compound (1-1) Polyfunctional acrylic compound/acrylic compound 1: Trimethylolpropane triacrylate, which is a trifunctional acrylic compound, viscosity 106 mPa·s, glass transition temperature 62° C., refractive index 1.472, boiling point 300°C or higher, product number SR351S manufactured by Sartomer.
Acrylic compound 2: polyethylene glycol 200 dimethacrylate, which is a bifunctional acrylic compound, viscosity 14 mPa·s, manufactured by Shin Nakamura Chemical Co., Ltd., product name A-200.
Acrylic compound 3: polyethylene glycol 200 diacrylate, which is a bifunctional acrylic compound, viscosity: 17 mPa·s, manufactured by Shin Nakamura Chemical Co., Ltd., product name 4G.

(1-2) Monofunctional acrylic compound/acrylic compound 4: Isobornyl acrylate which is a monofunctional acrylic compound, viscosity 8 mPa·s, glass transition temperature 97° C., boiling point 260° C., manufactured by Osaka Organic Chemical Industry Co., Ltd., product name IBXA.
Acrylic compound 5: dicyclopentanyl acrylate which is a monofunctional acrylic compound, viscosity 13 mPa·s, glass transition temperature 120° C., manufactured by Hitachi Chemical Co., Ltd., product name FA-513AS.
Acrylic compound 6: dicyclopentanyl methacrylate, viscosity 12 mPa·s, glass transition temperature 175° C., manufactured by Hitachi Chemical Co., Ltd., product name FA513M.
Acrylic compound 7: Acryloylmorpholine which is a monofunctional acrylic compound, viscosity 12 mPa·s, glass transition temperature 145° C., manufactured by KJ Chemicals Corporation.
-Acrylic compound 8: hydroxyethyl acrylamide, which is a monofunctional acrylic compound, viscosity 280 mPas, glass transition temperature 98°C.

(2) Thiol compound/thiol compound 1: pentaerythritol tetrakis(3-mercaptobutyrate). A tetrafunctional secondary thiol compound having four thiol groups in one molecule. Viscosity 1100 mPa·s (25° C.), product name Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK.
-Thiol compound 2: 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. A trifunctional secondary thiol compound having three thiol groups in one molecule. Viscosity 7500 mPa·s (25° C.), product name Karenz MT (registered trademark) NR1 manufactured by Showa Denko KK
-Thiol compound 3: 1,4-bis(3-mercaptobutyryloxy)butane. A bifunctional secondary thiol compound having two thiol groups in one molecule. Viscosity 21 mPa·s (25° C.), product name Karenz MT (registered trademark) BD1 manufactured by Showa Denko KK
-Thiol compound 4: pentaerythritol tetrakis (mercaptopropionate). A tetrafunctional primary thiol compound having four thiol groups in one molecule. Viscosity 430 mPa·s (25° C.), product name Karenz MT (registered trademark) PE1 manufactured by Sakai Chemical Industry Co., Ltd.

(3) Polymerization initiator/photopolymerization initiator 1: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Acylphosphine oxide photopolymerization initiator, manufactured by BASF Ltd., product name IrgacureTPO.
-Photopolymerization initiator 2: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one. Aminoacetophenone photopolymerization initiator, manufactured by BASF Ltd., product name Irgacure 907.
Photosensitizer 1: 2,4-diethylthioxanthen-9-one. Thioxanthone sensitizer.

(4) Hygroscopic agent (4-1) Zeolite particles 1
Zeolite particles 1 are produced by the following method, and have a D50 of 60 nm, a D90 of 110 nm and a pH of 11.

As the starting zeolite powder, 4A type zeolite/sodium ions having an average particle size of 5 μm were prepared, and 100 g of this zeolite powder and 100 g of ion-exchanged water were mixed to prepare a slurry.

400 g of zirconia beads having a particle size of 100 μm was put into this slurry, and then the zeolite powder in the slurry was crushed for 3 hours by a bead mill crusher, so that the average particle size of Na-based zeolite was 120 nm. At this time, the slurry flow rate is 10 kg/h and the slurry viscosity is 10 mPa·s.

Subsequently, the zirconia beads having a particle size of 100 μm were removed from the slurry, 400 g of zirconia beads having a particle size of 50 μm was put in place of the zirconia beads, and the Na-based zeolite in the slurry was crushed for 1 hour by a bead mill crusher to obtain a zeolite powder. The average particle size was 70 nm. At this time, the slurry flow rate is 10 kg/h and the slurry viscosity is 6 mPa·s.

Subsequently, the zirconia beads having a particle size of 50 μm were removed from the slurry, 450 g of zirconia beads having a particle size of 30 μm was put in place of the zirconia beads, and the zeolite powder in the slurry was crushed for 1 hour by a bead mill crusher to obtain an average of the zeolite powder. The particle size was 60 nm. At this time, the slurry flow rate is 10 kg/h and the slurry viscosity is 4 mPa·s.

Then, the slurry was left to stand 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 the particle size was adjusted by passing through a mesh to obtain zeolite particles 1.

The pH of the zeolite particles was measured by the following method. After putting 0.05 g of zeolite particles and 99.95 g of ion-exchanged water in a polyethylene bottle, the bottle was placed in a constant temperature bath 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 <LAQUATwin>B-711 manufactured by Horiba Ltd.

(4-2) Zeolite particles 2
Zeolite particles 2 are produced by the following method and have a D50 of 150 nm, a D90 of 250 nm and a pH of 11.

As the starting zeolite powder, 4A type zeolite/sodium ions having an average particle size of 5 μm were 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 of the zeolite particles 1 so that the average particle diameter was 150 nm.

Then, the slurry was left to stand 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.

(5) Dispersant/Dispersant 1: Lubrizol Co., Ltd., product name SOLSPERSE41000, a surfactant containing a phosphate group.

2. Evaluation test The following evaluation tests were carried out for the examples and comparative examples. The results are shown in the table.

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

2.2. Tackiness (curability)
By applying the composition on a smooth table and then irradiating it with light for 15 seconds under the conditions of a peak wavelength of 395 nm and an output of 100 mW/cm ² using an LED-UV irradiator manufactured by CCS Co., Ltd. Light cured. Atmosphere in which light is irradiated, in Examples 1-19 and Comparative Example 1, the atmosphere containing oxygen (oxygen concentration 210L / m ^3), Comparative Example 2 and 3, a nitrogen atmosphere (oxygen concentration 5L / m ³ ). Thereby, a film having a thickness of 10 μm was produced. The tester touched the surface of this film with a finger to determine the presence or absence of tack. As a result, the tester evaluated "A" when the tack was not felt and "C" when the tacker was felt. In Examples 1 to 19, it was found that the same curability as in Comparative Examples 2 and 3 in which light was irradiated in a nitrogen atmosphere could be achieved.

2.3. Transmittance The composition is applied to prepare a coating film, and this coating film is irradiated with light for 15 seconds under the conditions of a peak wavelength of 395 nm and about 100 mW/cm ² using an LED-UV irradiator manufactured by CCS Co., Ltd. Then, by photo-curing, a film having a thickness of 10 μm was produced. The atmosphere when irradiating light is the same as in 2.2. It is similar to the case of. The total light transmittance of this film according to JIS K7361-1 was measured.

2.4. Evaluation of Cured Product Outgas The outgas when the cured product of the composition was heated was sampled by the headspace method and measured by gas chromatography. 100 mg of the composition was placed in a vial for headspace, and the composition was cured by light irradiation using an LED-UV irradiator manufactured by CCS Co., Ltd. under conditions of a peak wavelength of 395 nm and about 100 mW/cm ^2. After that, the vial was sealed and heated at 80° C. for 30 minutes, and then the gas phase portion 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 it was 500 ppm or more was evaluated as "C".

2.5. Inkjet printability Using a model number MH2420 manufactured by Ricoh Co., Ltd. as an inkjet printer, the composition is put in a cartridge of the inkjet printer, and after confirming that the composition in the cartridge can be discharged from the nozzle of the inkjet printer, the composition is discharged from the nozzle. Was ejected to continuously print a test pattern. As a result, “A” indicates that the composition can be ejected for 1 hour and the ejection operation is stable, and “B” indicates that the composition can be ejected for 1 hour but the ejection operation is intermittently unstable. The case where the nozzle was clogged and the composition could not be discharged 1 hour before the discharge was started was evaluated as "C".

2.6. Adhesion A silicon nitride film (refractive index 1.81) having a thickness of 100 nm was formed on the surface of a quartz glass piece (size: 50 mm×25 mm×1 mm) by the plasma CVD method. The composition was applied onto this silicon nitride film to form a coating film having a thickness of 50 μm. This produced the 1st test piece.

A 100-nm-thick silicon nitride film (refractive index 1.81) was formed by plasma CVD on the surface of another piece of quartz glass (size 76 mm×52 mm×1 mm). This produced the 2nd test piece.

The silicon nitride film of the second test piece was overlaid on the coating film of the first test piece such that the size of the region where both of them contact each other was 25 mm×25 mm. Then, the coating film was cured by irradiating with light for 15 seconds under the condition of about 100 mW/cm ² using an LED-UV irradiator manufactured by CCS Co., Ltd. The atmosphere when irradiating light is the same as in 2.2. It is similar to the case of.

Next, the adhesion strength between the two quartz glass pieces was evaluated by performing a tensile shearing (pulling speed 5 mm/min) test according to JIS-K-6850.

2.7. Storage stability The composition was left for 1 month at a temperature of 40°C under a nitrogen atmosphere. The viscosity of the composition before the test and the viscosity of the composition after the test were measured by 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. The measurement was performed under the conditions of and the rate of change in viscosity was calculated from the result. The case where the rate of change was less than 5% was evaluated as "A", the case of 5% or more and less than 10% was evaluated as "B", and the case of 10% or more was evaluated as "C".

Claims (15)

A method of manufacturing a sealing material for covering a light emitting element, comprising:
Molding the light emitting element sealing composition, and then irradiating the light emitting element sealing composition with light under an atmosphere containing oxygen,
The light emitting element sealing composition contains a thiol compound (A), an acrylic compound (B), and a photopolymerization initiator (C),
Method of manufacturing encapsulant. The wavelength of the light is 385 nm or more,
The method for manufacturing the encapsulating material according to claim 1. Comprising molding the composition for sealing a light emitting device by an inkjet method,
The method for manufacturing the encapsulating material according to claim 1. The thiol compound (A) contains a polythiol compound (A1) having two or more thiol groups in one molecule,
The method for manufacturing the encapsulating material according to any one of claims 1 to 3. The viscosity of the thiol compound (A) at 25° C. is 2000 mPa·s or less,
The method for manufacturing the encapsulating material according to any one of claims 1 to 4. The content of the thiol compound (A) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) in the light emitting element sealing composition is 0.5% by mass or more and 10% by mass or less. is there,
The method for manufacturing the encapsulating material according to claim 1. The photopolymerization initiator (C) contains an aminoacetophenone initiator (C1),
The content of the aminoacetophenone initiator (C1) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is 1% by mass or more.
The method for manufacturing the encapsulating material according to claim 1. The photopolymerization initiator (C) contains a sensitizer (D),
The sensitizer (D) contains a thioxanthone sensitizer (D1),
The content of the thioxanthone sensitizer (D1) with respect to the photopolymerization initiator (C) is 1.0% by mass or more,
The method for manufacturing the encapsulating material according to any one of claims 1 to 7. The acrylic compound (B) contains a compound (B1) having an acryloyl group and a compound (B2) having a methacryloyl group,
The value of the mass ratio of the compound (B1) to the compound (B2) is 1 or more,
The method for manufacturing the encapsulating material according to claim 1. The acrylic compound (B) contains a nitrogen-containing acrylic compound (B43),
The content of the nitrogen-containing acrylic compound (B43) with respect to the total amount of the thiol compound (A) and the acrylic compound (B) is 10% by mass or more.
The method for manufacturing the encapsulating material according to claim 1. The light emitting element encapsulating composition further contains a hygroscopic agent (E),
The manufacturing method of the sealing material as described in any one of Claim 1 to 10. The moisture absorbent (E) contains zeolite particles,
The method for manufacturing a sealing material according to claim 11. The light emitting element sealing composition does not contain a solvent, or the content of the solvent is 0.1 mass% or less,
The method for manufacturing the encapsulating material according to claim 1. A method for manufacturing a light emitting device, comprising a light emitting element and a sealing material covering the light emitting element,
Manufacturing the encapsulant by the method for producing the encapsulant according to any one of claims 1 to 13,
Manufacturing method of light emitting device. The method for manufacturing a light emitting device according to claim 14, wherein the light emitting device is a display device.

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