Silicon-containing acrylic compound, photocurable resin composition, optical member, method for producing optical member, light-emitting device, and method for producing light-emitting device

Abstract

The silicon-containing acrylic compound has, in the molecule, a cyclic siloxane skeleton and an organic group having a (meth) acryloyl group bonded to the cyclic siloxane skeleton.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a silicon-containing acrylic compound, a photocurable resin composition, an optical member, a method for manufacturing an optical member, a light emitting device, and a method for manufacturing a light emitting device, and particularly relates to a novel silicon-containing acrylic compound, a photocurable resin composition containing the silicon-containing acrylic compound, an optical member produced from the photocurable resin composition, a method for manufacturing an optical member using the photocurable resin composition, a light emitting device provided with the optical member, and a method for manufacturing a light emitting device. BACKGROUND

[0002] In Patent Literature 1, it is described that by causing the acrylic compound contained in an ultraviolet curable resin composition for sealing an organic EL element to contain a compound having silicon in a molecular skeleton, the adhesion between a cured product of the ultraviolet curable resin composition and a member made of an inorganic material is improved.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent Application Publication No. 2020-053310 SUMMARY

[0006] The silicon-containing acrylic compound of one embodiment of the present disclosure has a cyclic siloxane skeleton and an organic group having a (meth)acryloyl group bonded to the cyclic siloxane skeleton in the molecule.

[0007] The photocurable resin composition of one embodiment of the present disclosure contains a radical polymerizable compound (A), and the radical polymerizable compound (A) contains the silicon-containing acrylic compound as a first radical polymerizable compound.

[0008] The optical member of one embodiment of the present disclosure includes a cured product of the photocurable resin composition.

[0009] The method for manufacturing an optical member of one embodiment of the present disclosure includes a step of curing the photocurable resin composition by irradiating light to the photocurable resin composition after the photocurable resin composition is ejected by an inkjet method.

[0010] The light emitting device of one embodiment of the present disclosure includes a light source and an optical member which transmits light emitted from the light source, and the optical member includes a cured product of the photocurable resin composition.

[0011] A method for manufacturing a light-emitting device according to one embodiment of the present disclosure is a method for manufacturing a light-emitting device including a light source and an optical component that transmits light emitted by the light source, and includes a step of manufacturing the optical component using the optical component manufacturing method.

[0012] One embodiment of the present disclosure can provide a silicon-containing acrylic compound capable of imparting flexibility to a cured product, a photocurable resin composition containing the silicon-containing acrylic compound and capable of imparting flexibility to a cured product, an optical component produced from the photocurable resin composition, a method for producing an optical component using the photocurable resin composition, a light-emitting device having the optical component, and a method for producing the light-emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 1 is a schematic cross-sectional view showing a light-emitting device in one embodiment of the present disclosure. DETAILED DESCRIPTION

[0014] The present disclosure provides a silicon-containing acrylic compound capable of imparting flexibility to a cured product, a photocurable resin composition containing the silicon-containing acrylic compound and capable of imparting flexibility to a cured product, an optical component produced from the photocurable resin composition, a method for producing an optical component using the photocurable resin composition, a light-emitting device having the optical component, and a method for producing the light-emitting device.

[0015] 1. Overview

[0016] Reference Figure 1 The embodiments of the present disclosure are described. It should be noted that the following embodiments are merely a portion of the various embodiments of the present disclosure. In addition, the following embodiments may be modified in various ways according to design, etc., as long as they can achieve the purpose of the present disclosure. The figures referenced below are schematic, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios.

[0017] The silicon-containing acrylic compound (a) (hereinafter also referred to as compound (a)) of the embodiment comprises a cyclic siloxane skeleton and an organic group bonded to the cyclic siloxane skeleton within its molecule. The organic group comprises a (meth)acryloyl group. In other words, the organic group comprises a (meth)acryloyl group as at least a portion of itself. The term "(meth)acryloyl" is a general term encompassing both acryloyl and methacryloyl groups and refers to at least one of these groups.

[0018] The compound (a) can improve the flexibility of a cured product obtained by curing a radically polymerizable composition containing the compound (a).

[0019] The light-curable resin composition (hereinafter, also referred to as composition (X)) of the embodiment contains a radical polymerizable compound (A) and a photoradical polymerization initiator (B). The radical polymerizable compound (A) contains the compound (a). Therefore, the compound (a) can improve the flexibility of a cured product obtained by curing the composition (X). Therefore, breakage at the time of deformation of the cured product can be suppressed, and for example, breakage of the cured product at the time of bending of the cured product in the case where the cured product is in a sheet shape can be suppressed.

[0020] The optical member of the embodiment contains a cured product of the composition (X). Therefore, the compound (a) can improve the flexibility of the optical member.

[0021] Note that the optical member in the embodiment refers to a member having a function of transmitting light. The optical member of the embodiment can be applied to, for example, a deformable light-emitting device typified by a foldable display by improving the flexibility. The optical member in the embodiment can be applied to, for example, a sealing portion of an organic EL light-emitting device in a display or the like. In addition, the optical member can be a color resist. That is, for example, a phosphor can be contained in the composition (X), and a color resist in a color filter can be produced from the composition (X). The color filter can be provided to a display device such as an organic EL display, a micro LED display, or the like, which is a light-emitting device.

[0022] The manufacturing method of the optical member of the embodiment includes a step of curing the composition (X) by irradiating the composition (X) with light after ejecting the composition (X) by an inkjet method.

[0023] The light-emitting device of the embodiment has a light source and an optical member that transmits light emitted from the light source, and the optical member contains a cured product of the composition (X). The light-emitting device is, for example, an organic EL light-emitting device. Note that EL refers to electroluminescence, and the organic EL light-emitting device refers to a light-emitting device having an organic EL element (organic light-emitting diode) as a light source. The light-emitting device can include a display device such as a display or the like. The light-emitting device can have a touch sensor. The light-emitting device can be, for example, a deformable light-emitting device such as a foldable display.

[0024] The manufacturing method of the light-emitting device of the embodiment includes a step of manufacturing an optical member in the light-emitting device by a method including a step of curing the composition (X) by irradiating the composition (X) with light after ejecting the composition (X) by an inkjet method.

[0025] 2. Silica-containing acrylic compound

[0026] As described above, the compound (a) has a cyclic siloxane skeleton and an organic group having a (meth)acryloyl group bonded to the cyclic siloxane skeleton in the molecule.

[0027] The compound (a) is represented by, for example, the following formula (1).

[0028] [Chemical Formula 1]

[0029]

[0030] In formula (1), n is an integer of 2 or more. n is, for example, 2 or more and 8 or less. n is more preferably 6 or less, and further preferably 4 or less. Each of R in the molecule is independently a monovalent aliphatic saturated hydrocarbon group having a carbon number of 1 or more and 5 or less, or an organic group having a (meth)acryloyl group, and two R bonded to one Si can together form a divalent aliphatic saturated hydrocarbon group having a carbon number of 3 or more and 6 or less. At least one of the plurality of R in the molecule is an organic group having a (meth)acryloyl group. The monovalent aliphatic saturated hydrocarbon group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a cyclopropyl group, or the like. The divalent aliphatic saturated hydrocarbon group is, for example, a butane-1,4-diyl group.

[0031] When the composition (X) containing the compound (a) is cured by radical polymerization to produce a cured product, the compound (a) can suppress curing shrinkage, and thus the cured product is less likely to be damaged. In addition, the compound (a) can improve the flexibility of the cured product.

[0032] Further, the compound (a) can improve the adhesion of the cured product to an inorganic material. Thus, in particular, in a case where the cured product is deformed together with an inorganic film in a state where the cured product overlaps the inorganic film, the cured product is less likely to be peeled from the inorganic film. Thus, the damage of the cured product at the time of deformation is further suppressed.

[0033] In addition, the relative dielectric constant of the inorganic material is relatively low, and thus the silicon-containing acrylic compound (a) is less likely to cause an increase in the relative dielectric constant of the composition (X) and the cured product.

[0034] The organic group having a (meth)acryloyl group (hereinafter, also referred to as organic group (g)) preferably has a cycloalkane skeleton. In this case, the flexibility of the cured product can be further improved. The cycloalkane skeleton is, for example, a cyclohexane skeleton.

[0035] In the organic group (g), for example, the (meth)acryloyl group is bonded to the cycloalkane skeleton via an oxygen atom.

[0036] The cycloalkane skeleton is, for example, directly bonded to a silicon atom in a cyclic siloxane skeleton, or bonded via a divalent saturated hydrocarbon group or the like organic group.

[0037] The organic group (g) has, for example, the structure of the following formula (2).

[0038] [Chemical Formula 2]

[0039]

[0040] In formula (2), R1and R2are each independently hydrogen or a (meth)acryl group, and at least one of R1and R2is a (meth)acryl group. In the formula, R3is a single bond, a divalent saturated hydrocarbon group, -C(=O)-, or -OC(=O)-. The carbon number of the divalent saturated hydrocarbon group is, for example, 1 or more and 10 or less.

[0041] In the organic group (g), it is preferable that both R1and R2be (meth)acryl groups. In this case, the glass transition temperature of the cured product can be increased by increasing the crosslinking density of the cured product. In addition, the relative dielectric constant of the inorganic material, the composition (X), and the cured product can be reduced by reducing or eliminating the intramolecular hydroxyl group in the inorganic material.

[0042] The organic group (g) preferably has a plurality of (meth)acryl groups in the molecule. In this case, the glass transition temperature of the cured product can be increased by increasing the crosslinking density of the cured product. The number of (meth)acryl groups in the organic group (g) is, for example, 2 or more and 8 or less. If the number of (meth)acryl groups in the organic group (g) is 4 or less, the viscosity of the silicon-containing acrylic compound (a) can be reduced.

[0043] The inorganic material contains, for example, at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0044] [Chemical Formula 3]

[0045]

[0046] [Chemical Formula 4]

[0047]

[0048] The inorganic material is synthesized, for example, by preparing a compound (hereinafter, also referred to as a compound (p)) having a cyclic siloxane skeleton and an organic group having an epoxy group bonded to the cyclic siloxane skeleton in the molecule, and reacting a (meth)acrylic acid with the epoxy group in the compound (p).

[0049] As the compound (p), a commercially available appropriate compound can be used. For example, as the compound (p), at least one selected from the group consisting of KR470, which is a cyclic siloxane 4-functional oligomer containing an alicyclic epoxy group, manufactured by Shin-Etsu Chemical Co., Ltd., X-22-2678, which is a cyclic siloxane 2-functional oligomer containing an alicyclic epoxy group, X-48-3300SX, which is a cyclic siloxane multi-functional (more than 4-functional) oligomer containing an alicyclic epoxy group, X-40-2728, which is a cyclic siloxane 2-functional oligomer containing a glycidyl group, and X-40-2701, which is a cyclic siloxane 4-functional oligomer containing a glycidyl group, and the like can be used.

[0050] The silicon-containing acrylic compound (a) is synthesized by reacting the compound (p) with the (meth)acrylic acid in an appropriate method. For example, in a reaction system containing the compound (p), the (meth)acrylic acid, and a catalyst, the epoxy group of the compound (p) is reacted with the (meth)acrylic acid, whereby the silicon-containing acrylic compound (a) is synthesized.

[0051] The catalyst is an appropriate compound that increases the reaction rate of the (meth)acrylic acid with the epoxy group. The catalyst contains, for example, at least one selected from the group consisting of a quaternary onium salt, a tertiary phosphine derivative, and a tertiary amine derivative, and the like. The quaternary onium salt contains, for example, at least one selected from the group consisting of tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide, and the like. The tertiary phosphine contains, for example, at least one selected from the group consisting of triphenylphosphine, tribenzylphosphine, trimethylphenylphosphine, and the like triaryl phosphine; tricyclohexylphosphine, and the like tricycloalkyl phosphine; and triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, and the like trialkyl phosphine, and the like. The tertiary amine contains, for example, at least one selected from the group consisting of triethylamine, tributylamine, and the like trialkyl amine; dimethylbenzylamine, diethylbenzylamine, and the like dialkyl aryl amine; and triethanolamine, and the like. The amount of the catalyst is, for example, 0.0001 mol or more and 1.0 mol or less, preferably 0.001 mol or more and 0.1 mol or less, relative to 1 mol of the (meth)acrylic acid.

[0052] It is also preferable to stabilize the reaction system by allowing a polymerization inhibitor such as hydroquinone or phenothiazine to be present in the reaction system.

[0053] A solvent can be present in the reaction system as needed. The solvent contains, for example, at least one selected from the group consisting of ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methoxybutyl acetate, diethylene glycol dimethyl ether, and methyl isobutyl ketone, and the like.

[0054] An organic sulfonic acid compound can be present in the reaction system. The organic sulfonic acid compound contains, for example, at least one selected from the group consisting of alkylsulfonic acids, hydroxyalkylsulfonic acids, carboxyalkylsulfonic acids, phenylsulfonic acids, phenolsulfonic acids, and carboxyphenylsulfonic acids. The alkylsulfonic acid contains, for example, methanesulfonic acid. The hydroxyalkylsulfonic acid contains, for example, at least one selected from the group consisting of hydroxyethanesulfonic acid and hydroxypropanesulfonic acid. The carboxyalkylsulfonic acid contains, for example, at least one selected from the group consisting of carboxyethanesulfonic acid and carboxypropanesulfonic acid. The phenylsulfonic acid contains, for example, at least one selected from the group consisting of benzenesulfonic acid, toluenesulfonic acid, and xylene sulfonic acid. The phenolsulfonic acid contains, for example, at least one selected from the group consisting of o-, m- or p-phenolsulfonic acid, and cresolsulfonic acid. The carboxyphenylsulfonic acid contains, for example, at least one selected from the group consisting of o-, m- or p-sulfobenzoic acid, and sulfoisophthalic acid. The weight of the organic sulfonic acid compound is preferably 0.5 to 3 times, more preferably 1 to 2 times, the weight of the catalyst.

[0055] The reaction of the epoxy group with the (meth)acrylic acid is preferably performed by heating the reaction system at, for example, 60 to 120°C for 5 to 20 hours.

[0056] In the reaction of the compound (p) with the (meth)acrylic acid, two molecules of the (meth)acrylic acid are preferably reacted with one epoxy group. In other words, one molecule of the (meth)acrylic acid is preferably reacted with one epoxy group to perform addition, and the thus generated hydroxyl group is further reacted with one molecule of the (meth)acrylic acid to perform addition. In this case, the intramolecular hydroxyl group of the compound (a) can be eliminated or reduced.

[0057] 3. Photocurable resin composition

[0058] As described above, the composition (X) contains the free radical polymerizable compound (A) and the photoradical polymerization initiator (B), and the free radical polymerizable compound (A) contains the compound (a).

[0059] The proportion of the compound (a) with respect to the composition (X) is preferably 5 mass% or more and 70 mass% or less. If the proportion is 5 mass% or more, the softness of the cured product can be particularly reduced. In addition, the adhesion of the cured product to inorganic materials can be further improved. If the proportion is 70 mass% or less, the increase in the viscosity of the composition (X) can be suppressed. The proportion is more preferably 15 mass% or more, and further preferably 20 mass% or more. In addition, the proportion is more preferably 65 mass% or less, and further preferably 50 mass% or less.

[0060] The free radical polymerizable compound (A) can contain a compound other than the compound (a).

[0061] The radical polymerizable compound (A) preferably contains, as the second radical polymerizable compound, a monofunctional radical polymerizable compound (b) (hereinafter, also referred to as compound (b)) having a nitrogen atom in the molecule.

[0062] The compound (b) has only one radical polymerizable functional group in the molecule and has a nitrogen atom. The compound (b) can further improve the adhesion of the cured product to the inorganic substance film. Therefore, in the case where the cured product is deformed together with the inorganic substance film in a state where the cured product overlaps the inorganic substance film, the cured product is less likely to peel off from the inorganic substance film. Thus, the breakage of the cured product at the time of deformation is further suppressed.

[0063] The compound (b) can improve the wettability of the composition (X) to the inorganic substance film. Therefore, the composition (X) is easily applied to the inorganic substance film and formed. In addition, the compound (b) can have a low viscosity. Therefore, the compound (b) is less likely to deteriorate the formability of the composition (X), or can improve the formability of the composition (X). In addition, the compound (b) can have a high reactivity. Therefore, unreacted components are less likely to remain at the time of curing of the composition (X), and thus the generation of outgassing from the cured product is suppressed.

[0064] The compound (b) preferably contains at least one selected from the group consisting of a compound having an oxazoline ring, a compound having a morpholine ring, a compound having a dimethylamino group, a compound having a diethylamino group, and a compound having a pyrrolidone ring. In this case, the adhesion of the cured product to the inorganic substance film can be further improved.

[0065] The compound having an oxazoline ring contains, for example, vinylmethyl oxazolidinone. The compound having a morpholine ring contains, for example, at least one selected from the group consisting of acryloyl morpholine and morpholinyl 4-acrylate, and the like. The compound having a dimethylamino group contains, for example, at least one selected from the group consisting of dimethyl acrylamide, dimethyl methyl acrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, and the like. The compound having a diethylamino group contains, for example, at least one selected from the group consisting of diethyl acrylamide and diethyl methyl acrylamide, and the like. The compound having a pyrrolidone ring contains, for example, N-vinyl-2-pyrrolidone.

[0066] Note that the compound (b) can contain a compound other than the above-described compounds, and for example, the compound (b) can contain a compound having a piperidine ring such as pentamethylpiperidyl methacrylate.

[0067] The compound (b) preferably contains vinylmethyl oxazolidinone. In this case, the breakage of the cured product can be further suppressed. It is presumed that this is because the strength and flexibility of the cured product can be improved by introducing an ester skeleton into the polymer of the radical polymerizable compound (A) using vinylmethyl oxazolidinone.

[0068] The proportion of the compound (b) in the composition (X) is preferably 3% by mass or more and 70% by mass or less, relative to the composition (X). If the proportion is 5% by mass or more, the breakage at the time of deformation of the cured product can be further suppressed. If the proportion is 70% by mass or less, the generation of outgassing from the cured product is suppressed, and problems such as bubbling and peeling are less likely to occur in optical members and the like including the cured product. The proportion is further preferably 5% by mass or more. In addition, the proportion is more preferably 50% by mass or less, further preferably 40% by mass or less, and further preferably 35% by mass or less.

[0069] The radical polymerizable compound (A) also preferably contains, as a third radical polymerizable compound, an acrylic compound (c) (hereinafter, also referred to as a compound (c)) having a chain saturated hydrocarbon skeleton having 5 or more and 25 or less in number of carbons and a (meth)acryloyl group in the molecule. The compound (c) contains, for example, a compound having a structure in which a (meth)acryloyloxy group is bonded to a monohydric alcohol having a chain saturated hydrocarbon skeleton having 5 or more and 25 or less in number of carbons. In this case, the relative dielectric constant of the composition (X) and the cured product can be reduced. In addition, the compound (c) is less likely to excessively increase the viscosity of the composition (X).

[0070] The chain saturated hydrocarbon skeleton in the compound (c) can be linear or branched.

[0071] The compound (c) contains, for example, an ester of a (meth)acrylic acid and a compound containing at least one of a monohydric alcohol having a structure in which a hydroxyl group is bonded to one end of a chain saturated hydrocarbon skeleton having 5 or more and 25 or less in number of carbons, and a dihydric alcohol having a structure in which hydroxyl groups are bonded to both ends of a chain saturated hydrocarbon skeleton. That is, for example, the compound (c) contains at least one selected from an ester of a (meth)acrylic acid and a monohydric alcohol, a monoester of a (meth)acrylic acid and a dihydric alcohol, and a diester of a (meth)acrylic acid and a dihydric alcohol.

[0072] The compound (c) contains, for example, at least one selected from the group consisting of 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,17-heptadecanediol di(meth)acrylate, 1,18-octadecanediol di(meth)acrylate, 1,19-nonadecanediol di(meth)acrylate, 1,20-icosanediol di(meth)acrylate, 1,21-heneicosanediol di(meth)acrylate, 1,22-docosanediol di(meth)acrylate, 1,23-tricosanediol di(meth)acrylate, 1,24-tetracosanediol di(meth)acrylate, 1,25-pentacosanediol di(meth)acrylate, isooctyl (meth)acrylate, isopentyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, cetyl (meth)acrylate, isooctyl (meth)acrylate, and tridecyl (meth)acrylate.

[0073] In order to reduce the relative dielectric constant, the number of carbons of the chain saturated hydrocarbon skeleton in the compound (c) is more preferably 6 or more, and further preferably 9 or more. In order to reduce the viscosity, the number of carbons of the chain saturated hydrocarbon skeleton in the compound (c) is more preferably 18 or less, and further preferably 14 or less.

[0074] The proportion of the compound (c) in the composition (X) is preferably 30% by mass or more and 85% by mass or less. If the proportion is 30% by mass or more, the relative dielectric constant of the cured product can be further reduced. If the proportion is 85% by mass or less, the adhesion to a substrate such as an inorganic material becomes good, and the advantage of further suppressing breakage at the time of deformation of the cured product is obtained. The proportion is further preferably 40% by mass or more. In addition, the proportion is more preferably 65% by mass or less, and further preferably 50% by mass or less.

[0075] The radical polymerizable compound (A) can contain a compound (hereinafter, also referred to as a compound (d)) other than any one of the compound (a), the compound (b), and the compound (c). The proportion of the compound (d) with respect to the composition (X) is, for example, 0% by mass or more and 10% by mass or less.

[0076] The compound (d) contains at least one of a multifunctional radical polymerizable compound (dl) having two or more radical polymerizable functional groups in a molecule (hereinafter, also referred to as compound (dl)) and a monofunctional radical polymerizable compound (d2) having only one radical polymerizable functional group in a molecule (hereinafter, also referred to as compound (d2)).

[0077] The compound (dl) can increase the reactivity of the composition (X). Therefore, the generation of an outgassing gas from the cured product can be suppressed. The compound (dl) can also increase the crosslinking density of the polymer of the radical polymerizable compound (A). Therefore, the glass transition temperature of the cured product can be increased, thereby increasing the heat resistance of the cured product.

[0078] The compound (d1) contains, for example, at least one of glycerol triacrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentaerythritol tetraacrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, propoxylated (3) glycerol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, dipentaerythritol hexaacrylate, ethylene glycol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, hydroxypivalic 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, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylated glycerol 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(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate.

[0079] The proportion of the compound (d1) with respect to the composition (X) is, for example, 10% by mass or less. In addition, the total proportion of the compounds having 2 or more radical polymerizable functional groups in the molecules, excluding the compound (a) and including the compound (d1), in the radical polymerizable compound (A) with respect to the composition (X) is, for example, 20% by mass or less.

[0080] The compound (d2) contains, for example, at least one compound selected from the group consisting of tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydioxyethyl acrylate, ethyl diethylene glycol acrylate, cyclic trimethylolpropane formal acrylate, imide acrylate, ethoxylated succinic acrylate, trifluoroethyl acrylate, omega-carboxy poly-caprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, diethylene glycol monobutyl ether acrylate, 3,3,5-trimethylcyclohexanol acrylate, caprolactone acrylate, ethoxylated (4) nonyl phenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, oxirane adduct of 2-phenoxyethyl acrylate, oxetane adduct of 2-phenoxyethyl acrylate, dicyclopentyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide, and 3-acryloyloxymethylcyclohexene oxide.

[0081] The compound (d2) can contain a monofunctional radical-polymerizable compound (d21) having two or more aromatic rings (hereinafter, also referred to as compound (d21)). This compound (d21) can further reduce the relative dielectric constant of the cured product of the composition (X), lower the viscosity of the composition (X), suppress the curing shrinkage at the curing of the composition (X), and increase the refractive index of the cured product.

[0082] The compound (d21) contains, for example, at least one of a compound represented by the following formula (5) and a compound represented by the following formula (6).

[0083] [Chemical Formula 5]

[0084]

[0085] [Chemical Formula 6]

[0086]

[0087] In formula (5), X1is hydrogen or a methyl group, Y1is a single bond or an alkylene group having 1 to 6 carbons, Z1is a single bond, S, or O, R1is H or a methyl group, L1is a single bond, an ester bond, or a thioester bond, n is 1 or 2, and in the case where L1is a single bond, n is 1, and m is 6 or 7. In formula (6), X2is a single bond or O, Z2is a single bond or O, R2is H or a methyl group, Y2is a single bond or an alkylene group having 1 to 6 carbons, and L2is a single bond or an ester bond.

[0088] The compound (d21) can contain a compound represented by the following formula (7). In formula (7), R1is H or CH3, X is O or S, and Z is a single bond or a divalent saturated hydrocarbon group. In the case where Z is a divalent saturated hydrocarbon group, the divalent saturated hydrocarbon group can be linear or branched. The compound can increase the refractive index of the cured product, and can also increase the strength and flexibility of the cured product. Thus, the breakage of the cured product can be further suppressed. More preferably, in formula (7), Z is a single bond, or Z is a divalent saturated hydrocarbon group and the number of carbons of the divalent saturated hydrocarbon group is 1 or more and 5 or less. In this case, the compound (d21) does not particularly increase the viscosity of the composition (X), and thus the compound (d21) does not particularly deteriorate the moldability of the composition (X).

[0089] [Chemical Formula 7]

[0090]

[0091] In the case where the composition (X) contains the compound (d21), the proportion of the compound (d21) with respect to the composition (X) is, for example, 30% by mass or more and 85% by mass or less.

[0092] The proportion of the compound (d2) with respect to the composition (X) is, for example, 10% by mass or less. In addition, the total proportion of the compounds having only one radical polymerizable functional group in the molecule among the radical polymerizable compounds (A), including the compound (d2), with respect to the composition (X) is, for example, 1% by mass or more and 20% by mass or less.

[0093] The photoradical polymerization initiator (B) is described. The photoradical polymerization initiator (B) contains, for example, at least one compound selected from the group consisting of an aromatic ketone compound, an acyloxyphosphine compound, an aromatic onium salt compound, an organic peroxide compound, a sulfur compound (a thioxanthone compound, a compound containing a thiophene group, and the like), a hexaarylbiimidazole compound, an oxime 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.

[0094] The ratio of the photoradical polymerization initiator (B) to the radical polymerizable compound (A) is preferably 6% by mass or more. In this case, the composition (X) can have good photocurability and can also have good photocurability in an atmospheric atmosphere. The ratio is more preferably 7% by mass or more and further preferably 8% by mass or more. In addition, the ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and further preferably 18% by mass or less.

[0095] The photoradical polymerization initiator (B) can include a photoradical polymerization initiator having photobleaching properties. In this case, the cured product of the composition (X) can have good light transmittance. The ratio of the photoradical polymerization initiator having photobleaching properties to the radical polymerizable compound (A) is preferably 3% by mass or more. The ratio is more preferably 7% by mass or more and further preferably 8% by mass or more. In addition, the ratio is, for example, 30% by mass or less, preferably 25% by mass or less, and further preferably 20% by mass or less.

[0096] The photoradical polymerization initiator having photobleaching properties contains, for example, at least one of a compound having photobleaching properties among an acyloxyphosphine-based photoinitiator and an oxime ester-based photoinitiator.

[0097] The photoradical polymerization initiator (B) can include a component having a sensitizer skeleton in the molecule. The sensitizer skeleton contains, for example, at least one of a 9H-thioxanthone skeleton and an anthracene skeleton. That is, the photoradical polymerization initiator (B) preferably includes a component having at least one of a 9H-thioxanthone skeleton and an anthracene skeleton.

[0098] The composition (X) can contain a polymerization accelerator in addition to the photoradical polymerization initiator (B). The polymerization accelerator contains, for example, an amine compound such as ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and butoxyethyl p-dimethylaminobenzoate. Note that the component that the polymerization accelerator can contain is not limited to the above components.

[0099] The composition (X) preferably contains no solvent or the content of the solvent is 1 mass% or less. In this case, it is difficult to generate an outgassing gas originating from the solvent from the composition (X) and the cured product of the composition (X). In addition, in the production of the optical member and the light-emitting device, it is possible to omit a drying step for removing the solvent from the composition (X) and the cured product. It is also possible to perform a drying step for removing the solvent from at least one of the composition (X) and the cured product, in which case, at least one of the reduction of the heating temperature and the shortening of the heating time in the drying step can be achieved. Thus, it is possible to prevent the generation of an outgassing gas from the optical member without reducing the production efficiency of the optical member and the light-emitting device. Furthermore, particularly in the case where the composition (X) is shaped by the inkjet method, it is difficult to cause a reduction in the thickness due to the volatilization of the solvent from the shaped composition (X), and thus a reduction in the thickness of the optical member is difficult to occur. Thus, while the composition (X) is shaped by the inkjet method, it is possible to ensure the thickness of the optical member to be as large as possible. The content of the solvent is more preferably 0.5 mass% or less, further preferably 0.3 mass% or less, and particularly preferably 0.1 mass% or less. It is particularly preferable that the composition (X) contains no solvent or contains only a solvent that is inevitably mixed.

[0100] The composition (X) can further contain any additive other than the inorganic filler, the hygroscopic material, the dispersant, and the silane coupling agent described above, within a range that does not substantially hinder the object of the present disclosure.

[0101] In the case where the composition (X) contains the inorganic filler, the inorganic filler is preferably of a nano size. In this case, it is possible to increase the refractive index of the cured product while maintaining the good transparency (visible light transmittance) of the cured product. The nano size means that the average particle diameter is 1 nm or more and 1000 nm or less. The average particle diameter of the inorganic filler is preferably 30 nm or less, and more preferably 20 nm or less. In addition, the average particle diameter is preferably 5 nm or more, and more preferably 10 nm or more. Note that the average particle diameter is the median particle diameter, that is, the cumulative 50% particle diameter (D50), calculated from the measurement results based on the dynamic light scattering method. Note that, as the measurement device, Nanotrac (Japanese: Nano Torakku) Wave series by Microtrac BEL Corporation can be used.

[0102] In the present embodiment, the composition (X) can be used for the production of an optical member. The optical member is a member disposed on the path of light in an optical system. In the present embodiment, the composition (X) can be preferably used for the production of an optical member that transmits light. However, the use of the composition (X) is not limited to the production of an optical member, and the composition (X) can be applied to various uses that utilize its properties.

[0103] In the present embodiment, the composition (X) can have a low viscosity. Therefore, the composition (X) is excellent in formability. For example, the composition (X) can be formed by being ejected by an inkjet method. When a cured product or an optical member or the like is manufactured from the composition (X), it is preferable that the composition (X) is formed by being ejected by an inkjet method. That is, the composition (X) is preferably used for inkjet forming. In this case, the cured product and the optical member of the composition (X) can be manufactured with high positional accuracy. In addition, in the case where the composition (X) is formed by being ejected by an inkjet method, foreign matter is less likely to be mixed into the composition (X) and the cured product thereof, as compared with the case where the composition (X) is formed by a printing method such as a screen printing method, and therefore, the yield is less likely to be deteriorated when the optical member is manufactured.

[0104] The viscosity of the composition (X) at 40°C is preferably 16 mPa-s or less. In this case, the viscosity of the composition (X) can be lowered by slightly heating the composition (X) regardless of the viscosity of the composition (X) at normal temperature. Therefore, the composition (X) can be easily formed, particularly by being ejected by an inkjet method, if heating is performed. In addition, since the composition (X) can be made low in viscosity without greatly heating the composition (X), a change in the composition of the composition (X) due to volatilization of a component in the composition (X) is less likely to occur. The viscosity is also preferably 1 mPa-s or more, more preferably 5 mPa-s or more.

[0105] The viscosity of the composition (X) at 25°C is also preferably 50 mPa-s or less. The viscosity of the composition (X) at 25°C is more preferably 40 mPa-s or less, further preferably 30 mPa-s or less, particularly preferably 28 mPa-s or less. The viscosity is also preferably 1 mPa-s or more, still more preferably 5 mPa-s or more, more preferably 10 mPa-s or more, further preferably 20 mPa-s or more. In these cases, the composition (X) can be easily formed at normal temperature, particularly by an inkjet method.

[0106] The low viscosity of the composition (X) can be achieved by appropriately adjusting the composition of the radical polymerizable compound (A) within the ranges described above. Note that the method and conditions for measuring the viscosity of the composition (X) are described in detail in the column of Examples described later.

[0107] The proportion of the evolved gas generated when the cured product of the composition (X) is heated at 110°C for 30 minutes is preferably 25 ppm or less. That is, the curability of the composition (X) can be improved according to the present embodiment, and thus the proportion of the evolved gas generated from the cured product is preferably 25 ppm or less. In this case, the evolved gas is less likely to be generated from the cured product. Therefore, for example, a void caused by the evolved gas is less likely to be generated in a light-emitting device provided with an optical member formed of the cured product. Thus, water and oxygen are less likely to reach the light-emitting element through the void, and the light-emitting element is less likely to be deteriorated by water and oxygen. The proportion of the evolved gas is particularly preferably 15 ppm or less.

[0108] The reduction of the proportion of the evolved gas generated from the cured product of the composition (X) can be achieved by appropriately adjusting the composition of the radically polymerizable compound (A) within the range described above. Note that the method of measuring the proportion of the evolved gas is described in detail in the Examples described later.

[0109] The glass transition temperature of the cured product of the composition (X) is preferably 75°C or higher. That is, the composition (X) preferably has a property of becoming a cured product having a glass transition temperature of 75°C or higher by curing. In this case, the cured product can have good heat resistance. Therefore, for example, in the case where a process accompanied by an increase in temperature is performed on the cured product, the cured product is less likely to be deteriorated. Thus, for example, in the case where an inorganic film (e.g., the passivation layer 6) overlapping the optical member is made by an evaporation method such as a plasma CVD method, the optical member is less likely to be deteriorated even if the optical member is heated. In addition, by improving the heat resistance, the optical member can also be adapted to uses such as a vehicle-mounted use where the requirement for heat resistance is strict. The glass transition temperature of the cured product is more preferably 90°C or higher, further preferably 110°C or higher, and particularly preferably 125°C or higher. The glass transition temperature of the cured product can be achieved by appropriately adjusting the composition of the radically polymerizable compound (A) within the range described above.

[0110] The total light transmittance according to JIS K7361-1 of a cured product having a thickness of 10 μm made of the composition (X) is preferably 98.0% or more, and preferably 99.0% or more. The total light transmittance of the cured product can be achieved by appropriately adjusting the composition of the composition (X) within the range described above.

[0111] The cured product made of the composition preferably has a relative dielectric constant of 3.8 or less at a measurement frequency of 100 kHz. In this case, in the case where the cured product is applied to an optical member in a light-emitting device, the operation reliability of the light-emitting device can be improved. In particular, in the case where the cured product is applied to an optical member in a light-emitting device equipped with a touch sensor, the erroneous operation of the touch sensor can be suppressed. The cured product more preferably has a relative dielectric constant of 3.4 or less, and further preferably 3.0 or less. The relative dielectric constant of the cured product can be achieved by appropriately adjusting the composition of the composition (X) within the ranges described above.

[0112] 4. Optical member and light-emitting device

[0113] An example of the structure of a light-emitting device 1 equipped with an optical member made of the composition (X) will be described. The light-emitting device 1 is equipped with a light source and an optical member that transmits light emitted from the light source. For example, the light-emitting device 1 is equipped with a light-emitting element 4, a sealing material 5 that covers the light-emitting element 4, and a passivation layer 6. In this case, the light-emitting element 4 is the light source, the sealing material 5 is the optical member, and the passivation layer 6 is the inorganic film. The sealing material 5 overlaps the passivation layer 6.

[0114] The light-emitting element 4 contains, for example, a light-emitting diode. The light-emitting diode contains, for example, at least one of an organic EL element (organic light-emitting diode) and a micro light-emitting diode. In the case where the light-emitting element 4 contains an organic light-emitting diode, the light-emitting device 1 equipped with the light-emitting element 4 is, for example, an organic EL display. In the case where the light-emitting element 4 contains a micro light-emitting diode, the light-emitting device 1 equipped with the light-emitting element 4 is, for example, a micro LED display. Note that EL is an abbreviation for electroluminescence.

[0115] Reference Example Figure 1 An example of the structure of a light-emitting device 1 will be described. The light-emitting device 1 is of a top emission type. The light-emitting device 1 is equipped with a support substrate 2, a transparent substrate 3 that faces the support substrate 2 with a space therebetween, a light-emitting element 4 that is located on a surface of the support substrate 2 facing the transparent substrate 3, and a passivation layer 6 and a sealing material 5 that cover the light-emitting element 4.

[0116] The support substrate 2 is made of, for example, a resin material, but is not limited thereto. The transparent substrate 3 is made of a material having a light-transmitting property. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The light-emitting element 4 is equipped with, for example, a pair of electrodes 41, 43 and an organic light-emitting layer 42 located between the electrodes 41, 43. The organic light-emitting layer 42 is equipped with, for example, a hole-injection layer 421, a hole-transport layer 422, an organic light-emitting layer 423, and an electron-transport layer 424, which are stacked in the above order.

[0117] The light emitting device 1 has 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 has partition walls 7. The partition walls 7 are located on the support substrate 2 to separate two adjacent light emitting elements 4. The partition walls 7 are produced, for example, by molding a photosensitive resin material using a photolithography method. The element array 9 also has connection wirings 8 that electrically connect the electrodes 43 and the electron transport layers 424 of adjacent light emitting elements 4 to each other. The connection wirings 8 are provided on the partition walls 7.

[0118] The passivation layer 6 corresponds to an inorganic film. The passivation layer 6 is preferably produced from silicon nitride or silicon oxide, and is particularly preferably produced from silicon nitride. In the case of silicon nitride, the passivation layer 6 has a function of preventing the diffusion of moisture and oxygen from the outside. Figure 1 In the example shown, the passivation layer 6 includes a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the light emitting elements 4 by covering the element array 9 in a state of directly contacting the element array 9. The second passivation layer 62 is disposed at a position opposite to the element array 9 with respect to the first passivation layer 61, and is spaced apart from the first passivation layer 61. A 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 elements 4 and the sealing material 5 that covers the light emitting elements 4.

[0119] Further, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is produced, for example, from a transparent resin material. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 can be the same as or different from that of the sealing material 5.

[0120] A method of producing the sealing material 5 using the composition (X) and a method of manufacturing the light emitting device 1 will be described.

[0121] In the present embodiment, it is preferable that the sealing material 5 be produced by curing the composition (X) by irradiation with ultraviolet rays after the composition (X) is jetted by the inkjet method to be shaped into a film. In the present embodiment, the composition (X) can be jetted by the inkjet method to be shaped.

[0122] In the case where the composition (X) has sufficiently low viscosity at ordinary temperature, for example, the viscosity at 25°C is 30 mPa-s or less, particularly 16 mPa-s or less, the composition (X) can be shaped by the inkjet method without heating. In the case where the composition (X) is low-viscosity-ized by heating, the composition (X) can be shaped by the inkjet method after the composition (X) is heated. As described above, in the case where the viscosity of the composition (X) at 40°C is particularly 16 mPa-s or less, the composition (X) can be low-viscosity-ized only by slightly heating the composition (X), and the low-viscosity-ized composition (X) can be jetted by the inkjet method. The heating temperature of the composition (X) is, for example, 20°C or higher and 50°C or lower.

[0123] More specifically, for example, first, the support substrate 2 is prepared. A partition wall 7 is formed on one face of the support substrate 2 by a photolithography method using, for example, a photosensitive resin material. Next, a plurality of light emitting elements 4 are provided on one face of the support substrate 2. The light emitting elements 4 can be formed by an appropriate method such as an evaporation method, a coating method, and the like. It is particularly preferable that the light emitting elements 4 are formed by a coating method such as an inkjet method. Thus, the element array 9 is formed on the support substrate 2.

[0124] Next, the first passivation layer 61 is provided on the element array 9. The first passivation layer 61 can be formed by an evaporation method such as a plasma CVD method.

[0125] Next, the composition (X) is jetted by the inkjet method to be shaped on the first passivation layer 61, and a coating film is formed. If the inkjet method is applied in both the formation of the light emitting elements 4 and the formation of the coating film, the manufacturing efficiency of the light emitting device 1 can be particularly improved. Subsequently, the coating film of the composition (X) is irradiated with light to be cured, and thus the sealing material 5 is formed.

[0126] In the irradiation of the composition (X) with light, the composition (X) can be irradiated with light in an oxygen-containing atmosphere such as an atmospheric air, or the composition (X) can be irradiated with light in a non-reactive atmosphere such as a nitrogen atmosphere.

[0127] Next, the second passivation layer 62 is provided on the sealing material 5. The second passivation layer 62 can be formed by an evaporation method such as a plasma CVD method.

[0128] Next, after a light-curable resin material is provided on one face of the support substrate 2 to cover the second passivation layer 62, the transparent substrate 3 is overlapped on the resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

[0129] Next, ultraviolet rays are irradiated from the outside to the transparent substrate 3. The ultraviolet rays pass through the transparent substrate 3 and reach the photocurable resin material. Thus, the photocurable resin material is cured, and the second sealing material 52 is produced.

[0130] The thickness of the sealing material 5 is, for example, 1 μm or more and 50 μm or less. The thickness of the sealing material 5 is more preferably 20 μm or less, and further preferably 15 μm or less. In this case, by making the sealing material 5 thin, the light emitting device 1 can be made thin, and a light emitting device 1 having flexibility, i.e., capable of being bent, can also be obtained. In addition, in order to effectively suppress moisture from reaching the light emitting element 4 with the sealing material 5, the thickness of the sealing material 5 is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 8 μm or more.

[0131] The thickness of the passivation layer 6 overlapping the sealing material 5 is, for example, 0.1 μm or more and 2 μm or less. As described above, in the case where the passivation layer 6 includes the first passivation layer 61 and the second passivation layer 62, the thickness of each of the first passivation layer 61 and the second passivation layer 62 is preferably 0.1 μm or more and 2 μm or less.

[0132] The light emitting device 1 can be a deformable light emitting device 1 such as a foldable display. In the embodiment, the sealing material 5 has flexibility, and has high adhesion to the passivation layer 6 which is an inorganic film, and thus even if the light emitting device 1 is deformed by being bent or the like, breakage of the sealing material 5 can be suppressed.

[0133] The light emitting device can also be provided with a touch sensor. In the embodiment, the relative dielectric constant of the sealing material 5 can be reduced, and thus malfunction of the touch sensor can be suppressed.

[0134] 5. Mode

[0135] The silicon-containing acrylic compound (a) of the first mode has a cyclic siloxane skeleton and an organic group (g) having a (meth)acryloyl group bonded to the cyclic siloxane skeleton in the molecule.

[0136] According to this mode, the flexibility of the cured product of the composition containing the silicon-containing acrylic compound (a) can be improved.

[0137] In the second mode, the organic group (g) has a cycloalkane skeleton on the basis of the first mode.

[0138] According to this mode, the flexibility of the cured product of the composition containing the silicon-containing acrylic compound (a) can be further improved.

[0139] In the third mode, in the organic group (g), the (meth)acryloyl group is bonded to the cycloalkane skeleton via an oxygen atom on the basis of the second mode.

[0140] In the fourth mode, in any one of the first to third modes, the silicon-containing acrylic compound (a) has a plurality of (meth)acryloyl groups in the molecule.

[0141] According to this mode, the glass transition temperature of the cured product of the composition containing the silicon-containing acrylic compound (a) can be increased.

[0142] In the fifth mode, on the basis of the fourth mode, the number of (meth)acryloyl groups in the molecule is 2 or more and 4 or less.

[0143] According to this mode, the viscosity increase of the silicon-containing acrylic compound (a) and the composition containing the silicon-containing acrylic compound (a) is suppressed, and the glass transition temperature of the cured product of the composition can be increased.

[0144] The sixth mode of the photocurable resin composition contains a radical polymerizable compound (A) containing the silicon-containing acrylic compound (a) of any one of the first to fifth modes as a first radical polymerizable compound.

[0145] According to this mode, the softness of the cured product of the photocurable resin composition can be increased by the silicon-containing acrylic compound (a).

[0146] In the seventh mode, on the basis of the sixth mode, the photocurable resin composition further contains a photoradical polymerization initiator (B).

[0147] In the eighth mode, on the basis of the sixth or seventh mode, the radical polymerizable compound (A) further contains a monofunctional radical polymerizable compound (b) having a nitrogen atom in the molecule as a second radical polymerizable compound.

[0148] According to this mode, the adhesion of the cured product of the photocurable resin composition to inorganic material can be increased.

[0149] In the ninth mode, on the basis of any one of the sixth to eighth modes, the radical polymerizable compound (A) further contains an acrylic compound (c) having a chain saturated hydrocarbon skeleton having a carbon number of 5 or more and 25 or less and a (meth)acryloyl group in the molecule as a third radical polymerizable compound.

[0150] According to this mode, the relative dielectric constant of the cured product of the photocurable resin composition can be reduced.

[0151] In the tenth mode, on the basis of any one of the sixth to ninth modes, the viscosity of the photocurable resin composition at 25°C is 50 mPa-s or less.

[0152] According to this aspect, the photocurable resin composition can have good formability and can be formed by being ejected using an inkjet method.

[0153] The optical member of the eleventh aspect includes a cured product of the photocurable resin composition of any one of the sixth to tenth aspects.

[0154] According to this aspect, the softness of the optical member is improved, and breakage of the optical member at the time of deformation can be suppressed.

[0155] The manufacturing method of the optical member of the twelfth aspect includes a step of curing the photocurable resin composition by irradiating the photocurable resin composition with light after the photocurable resin composition of any one of the sixth to tenth aspects is ejected using an inkjet method.

[0156] According to this aspect, the optical member can be manufactured with good positional accuracy, and the yield rate is less likely to deteriorate.

[0157] The light emitting device (1) of the thirteenth aspect includes a light source and an optical member that transmits light emitted from the light source, and the optical member includes a cured product of the photocurable resin composition of any one of the sixth to tenth aspects.

[0158] According to this aspect, the softness of the optical member is improved, and breakage of the optical member at the time of deformation can be suppressed.

[0159] The manufacturing method of the light emitting device (1) of the fourteenth aspect is a method of manufacturing a light emitting device including a light source and an optical member that transmits light emitted from the light source, and the manufacturing method of the light emitting device includes a step of manufacturing the optical member by the method of the twelfth aspect.

[0160] According to this aspect, the optical member in the light emitting device (1) can be manufactured with good positional accuracy, and the yield rate is less likely to deteriorate.

[0161] Example

[0162] 1. Synthesis of a silicon-containing acrylic compound

[0163] (1) Synthesis Example 1

[0164] In a 4-port flask equipped with a stirring blade, a condenser, and a thermometer, 300 parts (1.5 parts by equivalent) of a product number KR470 (epoxy equivalent 200 g / mol) manufactured by Shikoku Chemicals Corporation and 258 parts (3 parts by equivalent) of methacrylic acid (molecular weight 86 g / mol) manufactured by Shikoku Chemicals Corporation were first put in and homogenized by stirring. Next, 2.0 parts of triphenylphosphine, 0.2 parts of hydroquinone monomethyl ether, and 2.0 parts of phenol sulfonic acid were put in and mixed to dissolve the solid components. The liquid temperature was raised to 80°C to 90°C, and then the reaction was performed at a temperature range of 80°C to 90°C for 10 hours. In this way, a compound having a structure shown in Formula (4) was synthesized.

[0165] The compound obtained by the above synthesis was analyzed by an infrared spectrometer (FTIR), and as a result, it was confirmed that there was no peak derived from an epoxy group (902 cm -1 ), and a peak derived from C=0 (1731 cm -1 ) was generated. Thus, it was confirmed that the compound obtained by the above synthesis was a compound having a structure represented by formula (4).

[0166] (2) Synthesis Example 2

[0167] Instead of the product number KR470 manufactured by Shin-Etsu Chemical Co., Ltd., a product number X-22-2678 (epoxy equivalent weight: 290 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used in 435 parts (1.5 equivalent parts). Other than this, a compound having a structure represented by formula (3) was synthesized by the same method as in Synthesis Example 1.

[0168] (3) Synthesis Example 3

[0169] Instead of the product number KR470 manufactured by Shin-Etsu Chemical Co., Ltd., a product number X-40-2728 (epoxy equivalent weight: 200 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used in 300 parts (1.5 equivalent parts). Other than this, a silicon-containing acrylic compound having a cyclic siloxane skeleton and four methacryloyl groups in the molecule and not having a naphthene skeleton was synthesized by the same method as in Synthesis Example 1.

[0170] (4) Synthesis Example 4

[0171] Instead of the product number KR470 manufactured by Shin-Etsu Chemical Co., Ltd., a product number X-40-2669 (epoxy equivalent weight: 280 g / mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used in 420 parts (1.5 equivalent parts). Other than this, a silicon-containing acrylic compound having a linear siloxane skeleton and four methacryloyl groups in the molecule and not having a naphthene skeleton was synthesized by the same method as in Synthesis Example 1.

[0172] 2. Preparation of Composition

[0173] The compositions of the examples and comparative examples were prepared by mixing the components shown in the following table. Details of the components shown in the table are described below.

[0174] - Silicon-containing acrylic compound #1: a compound having a structure represented by formula (11) synthesized in Synthesis Example 1.

[0175] - Silicon-containing acrylic compound #2: a compound having a structure represented by formula (12) synthesized in Synthesis Example 2.

[0176] Silicon-containing acrylic compound #3: a compound synthesized in Synthesis Example 3, which has a cyclic siloxane skeleton and four methacryloyl groups in the molecule, and does not have a naphthene skeleton.

[0177] Silicon-containing acrylic compound #4: a compound synthesized in Synthesis Example 4, which has a linear siloxane skeleton and four methacryloyl groups in the molecule, and does not have a naphthene skeleton.

[0178] Silicon-containing acrylic compound #5: dimethyl silicone methacrylate. Product No. X-22-164A manufactured by Shin-Etsu Chemical Co., Ltd.

[0179] N-containing monofunctional compound #1: vinyl methyl oxazolidinone. Manufactured by BASF Co. Product name VMOX.

[0180] N-containing monofunctional compound #2: acryloyl morpholine. Manufactured by KJ CHEMICALS Co. Product name ACMO.

[0181] N-containing monofunctional compound #3: N,N-dimethyl acrylamide. Manufactured by KJ CHEMICALS Co. Product name DMAA.

[0182] Acrylic compound #1: 1,12-dodecanediol dimethacrylate. Manufactured by Sartomer Co. Product name SR262.

[0183] Acrylic compound #2: 1,9-nonanediol diacrylate. Manufactured by Osaka Organic Chemical Industry Co. Product name Viscoat #260.

[0184] Acrylic compound #3: isostearyl acrylate. Manufactured by Osaka Organic Chemical Industry Co. Product name ISTA.

[0185] Acrylic compound #4: cetyl acrylate. Manufactured by NOF Co. Product name Blemmer CA.

[0186] Acrylic compound #5: tripropylene glycol diacrylate. Manufactured by Osaka Organic Chemical Industry Co. Product name Viscoat #310HP.

[0187] Acrylic compound #6: a compound represented by the following formula (8). Manufactured by Kyoeisha Chemical Co. Product name Light Acrylate NMT-A.

[0188] [Formula 8]

[0189]

[0190] - Photopolymerization initiator: acyloxyphosphine-based photopolymerization initiator. Manufactured by IGM Resins B.V. Product name: Omnirad TPO H.

[0191] - Antioxidant: manufactured by BASF. Product name: Irganox 1010.

[0192] - Leveling agent: manufactured by BYK-Chemie. Product name: BYK330.

[0193] 3. Evaluation test

[0194] (1) Relative dielectric constant

[0195] A coating film of the composition having a thickness of 10 μm was produced on an aluminum substrate having a size of 80 mm x 40 mm x 1 mm t. The coating film was cured by irradiating ultraviolet rays for 15 seconds at 100 mW / cm 2 using an LCR meter (manufactured by Agilent, "E4980A") and a jig (16034 test jig) under the condition of a measurement frequency of 100 kHz.

[0196] (2) Viscosity at 25°C

[0197] The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model DHR-2) under the condition of a temperature of 25°C and a shear rate of 1000 s -1 .

[0198] (3) Inkjet property

[0199] The composition was added to a cartridge of an inkjet printer (manufactured by Fuji Photo Film, model DMP2831), and a droplet of the composition was ejected from a nozzle of the inkjet printer under the condition of a temperature of 40°C and a frequency of 1 kHz. The droplet was observed with a high-speed camera. As a result, a case where the droplet was not separated was evaluated as "A", a case where a satellite droplet was separated from the original droplet and the satellite droplet and the original droplet were integrated to become one droplet again was evaluated as "B", and a case where the satellite droplet was separated from the original droplet and remained un-integrated was evaluated as "C".

[0200] (4) Curing property

[0201] The composition was measured with an infrared spectrophotometer (manufactured by Agilent Technologies, model Agilent Cary 610 FTIR microscope system), and thus an IR spectrum was obtained.

[0202] The coating composition was coated to form a coating film having a thickness of 10 μm, and the coating film was irradiated with light having a peak wavelength of 395 nm at an irradiation intensity of 0.5 W / cm 2 and a cumulative light amount of 1.5 J / cm 2 under a nitrogen atmosphere using a UV irradiator (USHIO ELECTRIC CO., LTD., Model Unijet E075IIHD). Subsequently, the composition after the irradiation with ultraviolet rays (cured product) was measured using the above-described infrared spectrometer, and thus an IR spectrum was obtained.

[0203] In each of the two IR spectra, the peak intensity of the absorption of the acryloyl group appearing at 810 cm -1 was measured. Based on the peak intensity I0of the coating film and the peak intensity II of the cured product, the reduction rate of the reactive functional group in the composition before and after the irradiation with ultraviolet rays was calculated using the formula {1- (I0- II) / I0} x 100 (%). The result was taken as the reaction rate, and the case where the reaction rate was 90% or more was evaluated as "A", the case where the reaction rate was 80% or more and less than 90% was evaluated as "B", and the case where the reaction rate was less than 80% was evaluated as "C".

[0204] (5) Evaluation of Evolved Gas

[0205] The evolved gas when the cured product of the composition was heated was sampled by a headspace method, and was measured using a gas chromatograph. Specifically, first, 100 mg of the composition was put in a headspace vial having a volume of 22 mL. Subsequently, the composition was irradiated with light having a peak wavelength of 395 nm at an irradiation intensity of 0.5 W / cm 2 and a cumulative light amount of 1.5 J / cm 2 under a nitrogen atmosphere using a UV irradiator (USHIO ELECTRIC CO., LTD., Model Unijet E075IIHD), and thus the composition was cured. After that, the vial was sealed. Subsequently, the composition was heated at 110°C for 30 minutes, and then the gas phase portion in the vial was introduced into the gas chromatograph and was analyzed. As a result, the concentration of the evolved gas generated from the composition was determined based on the peak area of the obtained chromatogram. The concentration of the evolved gas refers to the volume fraction of the evolved gas in the gas phase of the vial with respect to the volume of the vial (22 mL).

[0206] Note that the concentration of the evolved gas was determined using toluene as a reference substance. Specifically, two reference samples having toluene concentrations of 1000 ppm and 100 ppm were prepared by volatilizing toluene in a vial. Each of the reference samples was introduced into the gas chromatograph and was analyzed. Based on the peak areas of the two chromatograms thus obtained, the relationship between the peak area and the concentration was specified, and based on the result, the above-described concentration of the evolved gas was determined.

[0207] (6) Adhesion

[0208] A silicon oxynitride film (SiON film) as an inorganic film was formed on a glass slide by a CVD method to a thickness of 1 μm. The composition was applied to the inorganic film to form a coating film to a thickness of 10 μm, and light with a peak wavelength of 395 nm was irradiated to the coating film under a nitrogen atmosphere using a UV irradiator (USHIO Denki, Model Unijet E075IIHD) at an irradiation intensity of 0.5 W / cm 2 and a cumulative light amount of 1.5 J / cm 2 . Thus, a film with a thickness of 10 μm was produced. As a result, the evaluation sample was produced, which comprised a substrate, an inorganic film, and a film.

[0209] (7) Flexibility

[0210] A silicon oxynitride film (SiON film) as an inorganic film was formed on a polyimide film as a substrate by a CVD method to a thickness of 1 μm. The composition was applied to the inorganic film to form a coating film to a thickness of 10 μm, and light with a peak wavelength of 395 nm was irradiated to the coating film under a nitrogen atmosphere using a UV irradiator (USHIO Denki, Model Unijet E075IIHD) at an irradiation intensity of 0.5 W / cm 2 and a cumulative light amount of 1.5 J / cm 2 . Thus, a film with a thickness of 10 μm was produced. As a result, the evaluation sample was produced, which comprised a substrate, an inorganic film, and a film.

[0211] The evaluation sample was subjected to a test in which it was repeatedly bent at a curvature radius of 1.5 mm, 2.0 mm, and 3.0 mm for 100,000 times.

[0212] As a result, the case where no abnormality such as peeling or cracking was observed in appearance after the test for 100,000 times at a curvature radius of 1.5 mm was evaluated as "A", the case where no abnormality was observed at a radius of 2.0 mm but was observed at 1.5 mm was evaluated as "B", the case where no abnormality was observed at a radius of 3.0 mm but was observed at 2.0 mm was evaluated as "C", and the case where an abnormality was observed at a radius of 3.0 mm was evaluated as "D".

[0213] (9) Glass transition temperature

[0214] A coating film was produced by coating the composition, and for the coating film, light of peak wavelength 395 nm was irradiated under an atmospheric air atmosphere using a UV irradiator (USHIO ELECTRIC CO., LTD., Model E075IIHD) at an irradiation intensity of 3 W / cm 2 and a cumulative light amount of 15 J / cm 2 , thereby making the coating film photocure, and a film of 500 μm in thickness was produced. The glass transition temperature of a sample cut from the film was measured using a viscoelasticity measuring device (Hitachi High-Tech Science Co., Ltd., Model DMA7100).

[0215] [Table 1]

[0216]

[0217] [Table 2]

[0218]

[0219] [Table 3]

[0220]

[0221] [Table 4]

[0222]

[0223] Explanation of Reference Signs

[0224] 1 Light-emitting device

[0225] 4 Light-emitting element (light source)

[0226] 5 Sealing material (optical member)

Claims

A silicon-containing acrylic compound comprising a cyclic siloxane skeleton and an organic group having a (meth)acryloyl group bonded to the cyclic siloxane skeleton in a molecule.

2. The silicon-containing acrylic compound according to claim 1, wherein The organic group has a cycloalkane skeleton.

3. The silicon-containing acrylic compound according to claim 2, wherein In the organic group, the (meth)acryloyl group is bonded to the cycloalkane skeleton via an oxygen atom. The silicon-containing acrylic compound according to claim 1 , comprising a plurality of (meth)acryloyl groups including the (meth)acryloyl group in the molecule.

5. The silicon-containing acrylic compound according to claim 4, wherein The number of the (meth)acryloyl groups in the molecule is 2 or more and 4 or less.

6. A photocurable resin composition comprising a radical polymerizable compound (A), The radically polymerizable compound (A) contains the silicon-containing acrylic compound according to any one of claims 1 to 5 as a first radically polymerizable compound. 7 . The photocurable resin composition according to claim 6 , further comprising a photoradical polymerization initiator (B).

8. The photocurable resin composition according to claim 6, wherein The radically polymerizable compound (A) further contains a monofunctional radically polymerizable compound having a nitrogen atom in the molecule as a second radically polymerizable compound.

9. The photocurable resin composition according to claim 6, wherein The radically polymerizable compound (A) further contains, as a third radically polymerizable compound, an acrylic compound having a chain-like saturated hydrocarbon skeleton having 5 to 25 carbon atoms and a (meth)acryloyl group in the molecule. 10 . The photocurable resin composition according to claim 6 , which has a viscosity at 25° C. of 50 mPa·s or less. 11 . An optical component comprising a cured product of the photocurable resin composition according to claim 6 . 12 . A method for producing an optical component, comprising the step of ejecting the photocurable resin composition according to claim 6 by an inkjet method and then irradiating the photocurable resin composition with light to cure the composition. 13 . A light-emitting device comprising a light source and an optical component that transmits light emitted from the light source, wherein the optical component comprises a cured product of the photocurable resin composition according to claim 6 .

14. A method for manufacturing a light emitting device, wherein: The light emitting device includes a light source and an optical component that transmits light emitted by the light source. The method for manufacturing a light emitting device comprises the step of manufacturing the optical component by the method according to claim 12 .

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