WO2024202791A1

WO2024202791A1 - Silicon-containing acrylic compound, photocurable resin composition, optical component, method for producing optical component, light-emitting device, and method for producing light-emitting device

Info

Publication number: WO2024202791A1
Application number: PCT/JP2024/006810
Authority: WO
Inventors: 祐輔浦岡; 裕基池上
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2023-03-31
Filing date: 2024-02-26
Publication date: 2024-10-03

Abstract

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

Description

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

This disclosure relates to a silicon-containing acrylic compound, a photocurable resin composition, an optical component, a method for manufacturing an optical component, a light-emitting device, and a method for manufacturing a light-emitting device, and more specifically to a novel silicon-containing acrylic compound, a photocurable resin composition containing this silicon-containing acrylic compound, an optical component made from the photocurable resin composition, a method for manufacturing an optical component using the photocurable resin composition, a light-emitting device including an optical component, and a method for manufacturing a light-emitting device.

Patent Document 1 describes that the acrylic compound in the UV-curable resin composition for sealing organic EL elements, which contains an acrylic compound and a photopolymerization initiator, contains a compound having silicon in the molecular skeleton, thereby improving adhesion between the cured product of the UV-curable resin composition and a component made of an inorganic material.

JP 2020-053310 A

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

The photocurable resin composition according to one embodiment of the present disclosure contains a radically polymerizable compound (A), and the radically polymerizable compound (A) contains the silicon-containing acrylic compound as a first radically polymerizable compound.

An optical component according to one embodiment of the present disclosure includes a cured product of the photocurable resin composition.

The method for manufacturing an optical component according to one embodiment of the present disclosure includes discharging the photocurable resin composition by an inkjet method and then irradiating the photocurable resin composition with light to cure it.

The light emitting device according to one aspect of the present disclosure includes a light source and an optical component that transmits light emitted by the light source, and the optical component includes a cured product of the photocurable resin composition.

A method for manufacturing a light-emitting device according to one aspect 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 manufacturing the optical component by the method for manufacturing the optical component.

One aspect of the present disclosure may 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 providing flexibility to a cured product, an optical component made from the photocurable resin composition, a method for manufacturing an optical component using the photocurable resin composition, a light-emitting device including the optical component, and a method for manufacturing the light-emitting device.

FIG. 1 is a schematic cross-sectional view showing a light-emitting device according to an embodiment of the present disclosure.

The objective of the present disclosure is to 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 providing a cured product with flexibility, an optical component made from the photocurable resin composition, a method for manufacturing an optical component using the photocurable resin composition, a light-emitting device including the optical component, and a method for manufacturing the light-emitting device.

1. Overview An embodiment of the present disclosure will be described with reference to FIG. 1. The following embodiment is merely a part of various embodiments of the present disclosure. In addition, the following embodiment can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. The figures referred to below are schematic diagrams, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios.

The silicon-containing acrylic compound (a) according to the embodiment (hereinafter also referred to as compound (a)) has a cyclic siloxane skeleton and an organic group bonded to the cyclic siloxane skeleton in the molecule. The organic group has a (meth)acryloyl group. That is, the organic group has a (meth)acryloyl group as at least a part of itself. The (meth)acryloyl group is a generic term that is a higher-level concept for an acryloyl group and a methacryloyl group, and means at least one of an acryloyl group and a methacryloyl group.

Compound (a) can increase the flexibility of the cured product obtained by curing a radically polymerizable composition containing compound (a).

The photocurable resin composition according to the embodiment (hereinafter also referred to as composition (X)) contains a radically polymerizable compound (A) and a photoradical polymerization initiator (B). The radically polymerizable compound (A) contains a compound (a). As a result, compound (a) can increase the flexibility of the cured product obtained by curing composition (X). As a result, damage to the cured product during deformation is suppressed, and for example, when the cured product is in the form of a sheet, damage to the cured product when the cured product is bent can be suppressed.

The optical component according to the embodiment includes a cured product of composition (X). Therefore, compound (a) can increase the flexibility of the optical component.

The optical component in the embodiment is a component that has the function of transmitting light. The optical component in the embodiment can be applied to a deformable light-emitting device, such as a foldable display, by increasing its flexibility. The optical component in the embodiment can be applied to a sealing portion of an organic EL light-emitting device in a display or the like. The optical component may also be a color resist. That is, for example, a phosphor may be contained in composition (X), and a color resist in a color filter may be produced from this composition (X). This color filter may be provided in a display device, such as an organic EL display or a micro LED display, which is a light-emitting device.

The method for manufacturing an optical component according to the embodiment includes discharging composition (X) by an inkjet method and then irradiating composition (X) with light to cure it.

The light-emitting device according to the embodiment includes a light source and an optical component that transmits light emitted by the light source, and the optical component includes a cured product of the composition (X). The light-emitting device is, for example, an organic EL light-emitting device. Note that EL stands for electroluminescence, and an organic EL light-emitting device is a light-emitting device that includes an organic EL element (organic light-emitting diode) as a light source. The light-emitting device may include a display device such as a display. The light-emitting device may include a touch sensor. The light-emitting device may be a deformable light-emitting device, such as a foldable display.

The method for manufacturing a light-emitting device according to the embodiment includes manufacturing an optical component in the light-emitting device by a method that includes discharging composition (X) by an inkjet method and then irradiating composition (X) with light to harden it.

2. Silicon-Containing Acrylic Compound As described above, the compound (a) has, in the molecule, a cyclic siloxane skeleton and an organic group having a (meth)acryloyl group bonded to the cyclic siloxane skeleton.

Compound (a) is, for example, represented by the following formula (1):

In formula (1), n is an integer of 2 or more. For example, n is 2 or more and 8 or less. It is more preferable that n is 6 or less, and even more preferable that n is 4 or less. Each R in the molecule is independently a monovalent aliphatic saturated hydrocarbon group having 1 to 5 carbon atoms or an organic group having a (meth)acryloyl group, and two R bonded to one Si may together form a divalent aliphatic saturated hydrocarbon group having 3 to 6 carbon atoms. At least one of the multiple R in the molecule is an organic group having a (meth)acryloyl group. Examples of the monovalent aliphatic saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. Examples of the divalent aliphatic saturated hydrocarbon group include a butane-1,4-diyl group.

When composition (X) containing compound (a) is cured by radical polymerization to produce a cured product, compound (a) can suppress cure shrinkage, making the cured product less likely to break. Compound (a) can also increase the flexibility of the cured product.

Furthermore, compound (a) can increase the adhesion between the cured material and the inorganic material. Therefore, when the cured material is deformed together with the inorganic film, particularly when the cured material is superimposed on the inorganic film, the cured material is less likely to peel off from the inorganic film. This further suppresses damage to the cured material when it is deformed.

In addition, the dielectric constant of inorganic materials is relatively low, so the silicon-containing acrylic compound (a) is unlikely to cause an increase in the dielectric constant of the composition (X) and the cured product.

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 increased. The cycloalkane skeleton is, for example, a cyclohexane skeleton.

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

The cycloalkane skeleton is bonded, for example, to a silicon atom in the cyclic siloxane skeleton either directly or via an organic group such as a divalent saturated hydrocarbon group.

The organic group (g) has, for example, a structure represented by the following formula (2):

In formula (2), R1 and R2 are each independently hydrogen or a (meth)acryloyl group, and at least one of R1 and R2 is a (meth)acryloyl group. In the formula, R3 is a single bond, a divalent saturated hydrocarbon group, -C(=O)-, or -OC(=O)-. The number of carbon atoms in the divalent saturated hydrocarbon group is, for example, 1 or more and 10 or less.

In the organic group (g), it is preferable that both R1 and R2 are (meth)acryloyl groups. In this case, the crosslink density of the cured product increases, which can increase the glass transition temperature of the cured product. In addition, by reducing or eliminating the hydroxyl groups in the molecule of the inorganic material, the relative dielectric constant of the inorganic material, composition (X), and the cured product can be reduced.

It is preferable that the organic group (g) has multiple (meth)acryloyl groups in the molecule. In this case, the crosslink density of the cured product increases, which can increase the glass transition temperature of the cured product. The number of (meth)acryloyl groups in the molecule of the organic group (g) is, for example, 2 to 8. If the number of (meth)acryloyl groups in the molecule of the organic group (g) is 4 or less, the viscosity of the silicon-containing acrylic compound (a) can be reduced.

The inorganic material contains, for example, at least one of the compounds shown in the following formula (3) and the compounds shown in the following formula (4).

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

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

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

The catalyst may be any suitable compound that improves the reaction rate between (meth)acrylic acid and an epoxy group. The catalyst contains at least one selected from the group consisting of, for example, quaternary onium salts, tertiary phosphine derivatives, and tertiary amine derivatives. The quaternary onium salt contains at least one selected from the group consisting of, for example, tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide. The tertiary phosphine contains at least one selected from the group consisting of, for example, triarylphosphines such as triphenylphosphine, tribenzylphosphine, and tritolylphosphine; tricycloalkylphosphines such as tricyclohexylphosphine; and trialkylphosphines such as triethylphosphine, tripropylphosphine, tributylphosphine, and trioctylphosphine. The tertiary amine contains at least one selected from the group consisting of, for example, trialkylamines such as triethylamine and tributylamine; dialkylarylamines such as dimethylbenzylamine and diethylbenzylamine; and triethanolamine. The amount of catalyst per mole of (meth)acrylic acid is, for example, 0.0001 moles or more and 1.0 moles or less, and preferably 0.001 moles or more and 0.1 moles or less.

It is also preferable to stabilize the reaction system by adding a polymerization inhibitor such as hydroquinone or phenothiazine to the reaction system.

A solvent may be present in the reaction system as necessary. The solvent may contain at least one selected from the group consisting of, for example, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methoxybutyl acetate, diethylene glycol dimethyl ether, and methyl isobutyl ketone.

An organic sulfonic acid compound may be present in the reaction system. The organic sulfonic acid compound contains at least one selected from the group consisting of, for example, alkyl sulfonic acid, hydroxyalkyl sulfonic acid, carboxyalkyl sulfonic acid, phenyl sulfonic acid, phenol sulfonic acid, and carboxyphenyl sulfonic acid. The alkyl sulfonic acid contains, for example, methane sulfonic acid. The hydroxyalkyl sulfonic acid contains at least one selected from the group consisting of, for example, hydroxyethyl sulfonic acid and hydroxypropyl sulfonic acid. The carboxyalkyl sulfonic acid contains at least one selected from the group consisting of, for example, carboxyethyl sulfonic acid and carboxypropyl sulfonic acid. The phenyl sulfonic acid contains at least one selected from the group consisting of, for example, benzene sulfonic acid, toluene sulfonic acid, and xylene sulfonic acid. The phenol sulfonic acid contains at least one selected from the group consisting of, for example, o-, m-, or p-phenol sulfonic acid, and cresol sulfonic acid. The carboxyphenylsulfonic acid contains at least one selected from the group consisting of, for example, o-, m-, or p-sulfobenzoic acid, and sulfoisophthalic acid. The weight of the organic sulfonic acid compound is preferably 0.5 to 3 times, and more preferably 1 to 2 times, the weight of the catalyst.

It is preferable to react the epoxy groups with (meth)acrylic acid by heating the reaction system at, for example, 60 to 120°C for 5 to 20 hours.

When reacting compound (p) with (meth)acrylic acid, it is preferable to react two molecules of (meth)acrylic acid with one epoxy group. In other words, it is preferable to react and add one molecule of (meth)acrylic acid to one epoxy group, and then react and add another molecule of (meth)acrylic acid to the hydroxyl group thus generated. In this case, it is possible to eliminate or reduce the number of hydroxyl groups in the molecule of compound (a).

3. Photocurable Resin Composition As described above, the composition (X) contains the radical polymerizable compound (A) and the photoradical polymerization initiator (B), and the radical polymerizable compound (A) contains the compound (a).

The ratio of compound (a) to composition (X) is preferably 5% by mass or more and 70% by mass or less. If the ratio is 5% by mass or more, the flexibility of the cured product can be particularly reduced. Also, the adhesion between the cured product and the inorganic material can be further increased. If the ratio is 70% by mass or less, an increase in the viscosity of composition (X) can be suppressed. This ratio is more preferably 15% by mass or more, and even more preferably 20% by mass or more. Also, this ratio is more preferably 65% by mass or less, and even more preferably 50% by mass or less.

The radically polymerizable compound (A) may contain a compound other than the compound (a).

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

Compound (b) has only one radically polymerizable functional group in the molecule and also has a nitrogen atom. Compound (b) can further increase the adhesion of the cured product to the inorganic film. Therefore, if the cured product is deformed together with the inorganic film while overlapping the inorganic film, the cured product is less likely to peel off from the inorganic film. This further suppresses damage to the cured product when it is deformed.

Compound (b) can increase the wettability of composition (X) with the inorganic film. This makes it easy to apply composition (X) onto an inorganic film and mold it. Compound (b) can also have a low viscosity. This makes it difficult for compound (b) to deteriorate the moldability of composition (X) or can improve the moldability of composition (X). Compound (b) can also have high reactivity. This makes it difficult for unreacted components to remain when composition (X) is cured, and therefore outgassing from the cured product can be suppressed.

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 film can be further improved.

The compound having an oxazoline ring contains, for example, vinylmethyloxazolidinone. The compound having a morpholine ring contains, for example, at least one selected from the group consisting of acryloylmorpholine and morpholin-4-yl acrylate. The compound having a dimethylamino group contains, for example, at least one selected from the group consisting of dimethylacrylamide, dimethylmethacrylamide, dimethylaminopropylacrylamide, and dimethylaminopropylmethacrylamide. The compound having a diethylamino group contains, for example, at least one selected from the group consisting of diethylacrylamide and diethylmethacrylamide. The compound having a pyrrolidone ring contains, for example, N-vinyl-2-pyrrolidone.

The compounds that compound (b) may contain are not limited to those mentioned above, and for example, compound (b) may contain a compound having a piperidine ring, such as pentamethylpiperidyl methacrylate.

It is preferable that compound (b) contains vinylmethyloxazolidinone. In this case, damage to the cured product can be further suppressed. This is presumably because vinylmethyloxazolidinone introduces an ester skeleton into the polymer of radically polymerizable compound (A), thereby increasing the strength and flexibility of the cured product.

The proportion of compound (b) in composition (X) is preferably 3% by mass or more and 70% by mass or less, based on composition (X). If this proportion is 5% by mass or more, damage to the cured product during deformation can be further suppressed. If this proportion is 70% by mass or less, outgassing from the cured product is suppressed, and problems such as blisters and peeling are less likely to occur in optical components containing the cured product. It is even more preferable for this proportion to be 5% by mass or more. It is even more preferable for this proportion to be 50% by mass or less, even more preferable for this proportion to be 40% by mass or less, and even more preferable for this proportion to be 35% by mass or less.

It is also preferable that the radically polymerizable compound (A) contains, as a third radically polymerizable compound, an acrylic compound (c) (hereinafter also referred to as compound (c)) having a chain-like saturated hydrocarbon skeleton with 5 to 25 carbon atoms in the molecule and a (meth)acryloyl group. Compound (c) includes, for example, a compound having a structure in which a (meth)acryloyloxy group is bonded to a chain-like saturated hydrocarbon skeleton with 5 to 25 carbon atoms. In this case, the relative dielectric constant of composition (X) and the cured product can be reduced. In addition, compound (c) is unlikely to excessively increase the viscosity of composition (X).

The chain saturated hydrocarbon skeleton in compound (c) may be linear or branched.

Compound (c) contains, for example, a compound containing at least one of a monol having a structure in which a hydroxyl group is bonded to one end of a chain-like saturated hydrocarbon skeleton having 5 to 25 carbon atoms, and a diol having a structure in which a hydroxyl group is bonded to each end of a chain-like saturated hydrocarbon skeleton, and an ester of (meth)acrylic acid. That is, for example, compound (c) contains at least one selected from the group consisting of an ester of a monol and (meth)acrylic acid, a monoester of a diol and (meth)acrylic acid, and a diester of a diol and (meth)acrylic acid.

Compound (c) is, for example, 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-un Decanediol 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, Contains at least one selected from the group consisting of candiol di(meth)acrylate, 1,19-nonadecanediol di(meth)acrylate, 1,20-icosanediol di(meth)acrylate, 1,21-henicosanediol di(meth)acrylate, 1,22-docosanediol di(meth)acrylate, 1,23-triicosanediol di(meth)acrylate, 1,24-tetracosanediol di(meth)acrylate, 1,25-pentacosanediol di(meth)acrylate, isooctyl (meth)acrylate, isoamyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, cetyl (meth)acrylate, isooctyl (meth)acrylate, and tridecyl (meth)acrylate.

To reduce the dielectric constant, the number of carbon atoms in the chain saturated hydrocarbon skeleton in compound (c) is preferably 6 or more, and more preferably 9 or more. To reduce the viscosity, the number of carbon atoms in the chain saturated hydrocarbon skeleton in compound (c) is preferably 18 or less, and even more preferably 14 or less.

The proportion of compound (c) in composition (X) is preferably 30% by mass or more and 85% by mass or less, based on composition (X). If this proportion is 30% by mass or more, the relative dielectric constant of the cured product can be further reduced. If this proportion is 85% by mass or less, there is an advantage that adhesion to the substrate such as an inorganic material is improved, and damage to the cured product during deformation is further suppressed. It is more preferable that this proportion is 40% by mass or more. It is also more preferable that this proportion is 65% by mass or less, and even more preferable that it is 50% by mass or less.

The radically polymerizable compound (A) may contain a compound other than compound (a), compound (b), or compound (c) (hereinafter also referred to as compound (d)). The ratio of compound (d) to composition (X) is, for example, 0% by mass or more and 10% by mass or less.

Compound (d) contains at least one of a polyfunctional radically polymerizable compound (d1) (hereinafter also referred to as compound (d1)) having two or more radically polymerizable functional groups in the molecule, and a monofunctional radically polymerizable compound (d2) (hereinafter also referred to as compound (d2)) having only one radically polymerizable functional group in the molecule.

Compound (d1) can increase the reactivity of composition (X). As a result, outgassing from the cured product can be suppressed. Compound (d1) can also increase the crosslink density of the polymer of radically polymerizable compound (A). As a result, the glass transition temperature of the cured product can be increased, thereby improving the heat resistance of the cured product.

Examples of compound (d1) include glycerin triacrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentaerythritol tetraacrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl)isocyanate, Anurate 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, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bispentaerythritol 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 glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated Contains at least one selected from the group consisting of silyl 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.

The ratio of compound (d1) to composition (X) is, for example, 10% by mass or less. In addition, the total ratio of compounds having two or more radically polymerizable functional groups in the molecule in radically polymerizable compound (A), excluding compound (a) and including compound (d1), to composition (X) is, for example, 20% by mass or less.

Compound (d2) is, for example, 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, methoxydixylethyl acrylate, ethyl di Glycol acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, diethylene glycol monobutyl ether acrylate, 3,3,5-trimethylcyclohexanol acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol Licor (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (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, It contains at least one compound selected from the group consisting of diethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide, and 3-acryloyloxymethylcyclohexene oxide.

Compound (d2) may contain a monofunctional radically 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 composition (X), lower the viscosity of composition (X), suppress the cure shrinkage during curing of composition (X), and increase the refractive index of the cured product.

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).

In formula (5), _X1 is hydrogen or a methyl group, _Y1 is a single bond or an alkylene group having 1 to 6 carbon atoms, _Z1 is a single bond, S or O, _R1 is H or a methyl group, _L1 is a single bond, an ester bond or a thioester bond, n is 1 or 2 except when _L1 is a single bond, n is 1 and m is 6 or 7. In formula (6), _X2 is a single bond or O, _Z2 is a single bond or O, _R2 is H or a methyl group, _Y2 is a single bond or an alkylene group having 1 to 6 carbon atoms, and _L2 is a single bond or an ester bond.

The compound (d21) may contain a compound represented by the following formula (7). In formula (7), R1 is H or _CH3 , X is O or S, and Z is a single bond or a divalent saturated hydrocarbon group. When Z is a divalent saturated hydrocarbon group, the divalent saturated hydrocarbon group may be linear or branched. This compound can increase the strength and flexibility of the cured product while increasing the refractive index of the cured product. Therefore, damage to the cured product can be further suppressed. It is more preferable that Z in formula (7) is a single bond, or Z is a divalent saturated hydrocarbon group and the carbon number of this divalent saturated hydrocarbon group is 1 to 5. In this case, the compound (d21) is particularly unlikely to increase the viscosity of the composition (X), and therefore the compound (d21) is particularly unlikely to deteriorate the moldability of the composition (X).

When composition (X) contains compound (d21), the ratio of compound (d21) to composition (X) is, for example, 30% by mass or more and 85% by mass or less.

The ratio of compound (d2) to composition (X) is, for example, 10% by mass or less. The total ratio of compounds having only one radically polymerizable functional group in the molecule, including compound (d2) in radically polymerizable compound (A), to composition (X) is, for example, 1% by mass or more and 20% by mass or less.

The photoradical polymerization initiator (B) will now be described. The photoradical polymerization initiator (B) contains at least one compound selected from the group consisting of aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The ratio of the photoradical polymerization initiator (B) to the radically 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 under an atmospheric environment. This ratio is more preferably 7% by mass or more, and even more preferably 8% by mass or more. This ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 18% by mass or less.

The photoradical polymerization initiator (B) may contain a photoradical polymerization initiator having photobleaching properties. In this case, the cured product of the composition (X) may have good light transmittance. The ratio of the photoradical polymerization initiator having photobleaching properties to the radically polymerizable compound (A) is preferably 3% by mass or more. This ratio is more preferably 7% by mass or more, and even more preferably 8% by mass or more. This ratio is, for example, 30% by mass or less, preferably 25% by mass or less, and even more preferably 20% by mass or less.

The photoradical polymerization initiator having photobleaching properties contains at least one of, for example, an acylphosphine oxide-based photoinitiator and a compound having photobleaching properties among oxime ester-based photoinitiators.

The photoradical polymerization initiator (B) may contain a component having a sensitizer skeleton in the molecule. The sensitizer skeleton includes, for example, at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton. In other words, it is preferable that the photoradical polymerization initiator (B) includes a component having at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton.

The composition (X) may 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, or butoxyethyl p-dimethylaminobenzoate. Note that the components that the polymerization accelerator may contain are not limited to those mentioned above.

The composition (X) preferably does not contain a solvent or the solvent content is 1% by mass or less. In this case, outgassing derived from the solvent is unlikely to occur from the composition (X) and the cured product of the composition (X). In addition, a drying process for removing the solvent from the composition (X) and the cured product during the production of optical components and light-emitting devices can be eliminated. A drying process for removing the solvent from at least one of the composition (X) and the cured product may be performed. In this case, at least one of the heating temperature and the heating time in the drying process can be reduced. Therefore, outgassing can be unlikely to occur from the optical components without reducing the production efficiency of the optical components and light-emitting devices. Furthermore, when the composition (X) is molded by ejecting it, especially by the inkjet method, the thickness is unlikely to decrease due to the evaporation of the solvent from the composition (X) after molding, and therefore the thickness of the optical components is unlikely to decrease. Therefore, the thickness of the optical components can be secured as large as possible while ejecting the composition (X) by the inkjet method to mold it. The content of the solvent is preferably 0.5% by mass or less, more 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 that is inevitably mixed in.

Composition (X) may further contain any additives other than those mentioned above, such as inorganic fillers, moisture absorbents, dispersants, and silane coupling agents, to the extent that the object of the present disclosure is not significantly impeded.

When composition (X) contains an inorganic filler, it is preferable that the inorganic filler is nano-sized. In this case, the cured product can have a high refractive index while maintaining good transparency (visible light transmittance) of the cured product. Nano-sized means that the average particle size is 1 nm or more and 1000 nm or less. The average particle size of the inorganic filler is preferably 30 nm or less, and more preferably 20 nm or less. In addition, this average particle size is preferably 5 nm or more, and more preferably 10 nm or more. Note that this average particle size is the median diameter calculated from the measurement results by dynamic light scattering method, that is, the cumulative 50% diameter (D50). Note that the Nanotrac NanotracWave series from Microtrac Bell Co., Ltd. can be used as a measuring device.

In this embodiment, the composition (X) can be used to manufacture an optical component. An optical component is a component that is disposed on the path of light in an optical system. In this embodiment, the composition (X) can be preferably used to manufacture an optical component that transmits light. However, the use of the composition (X) is not limited to the manufacture of optical components, and the composition (X) can be applied to various uses that utilize its properties.

In this embodiment, the composition (X) may have a low viscosity. Therefore, the moldability of the composition (X) is good. For example, the composition (X) may be molded by discharging it by an inkjet method. When producing a cured product or an optical part, etc. from the composition (X), it is preferable to mold the composition (X) by discharging it by an inkjet method. That is, the composition (X) is preferably for inkjet molding. In this case, the cured product and the optical part of the composition (X) can be produced with good positional accuracy. In addition, compared to molding by a printing method involving contact such as a screen printing method, when the composition (X) is molded by discharging it by an inkjet method, foreign matter is less likely to be mixed into the composition (X) and its cured product, and therefore the yield when manufacturing the optical part is less likely to deteriorate.

It is preferable that the viscosity of composition (X) at 40°C is 16 mPa·s or less. In this case, no matter what the viscosity of composition (X) is at room temperature, it is possible to reduce the viscosity by slightly heating composition (X). Therefore, composition (X) can be easily molded by heating, and in particular, it can be easily molded by discharging it by an inkjet method. In addition, since the viscosity of composition (X) can be reduced without significantly heating it, it is possible to make it difficult for the composition of composition (X) to change due to the volatilization of the components in composition (X). It is also preferable that this viscosity is 1 mPa·s or more, and more preferably 5 mPa·s or more.

It is also preferable that the viscosity of composition (X) at 25°C is 50 mPa·s or less. It is more preferable that the viscosity of composition (X) at 25°C is 40 mPa·s or less, even more preferable that it is 30 mPa·s or less, and particularly preferable that it is 28 mPa·s or less. It is also preferable that this viscosity is 1 mPa·s or more, more preferably 5 mPa·s or more, more preferably 10 mPa·s or more, and even more preferably 20 mPa·s or more. In these cases, composition (X) can be easily molded at room temperature, and in particular can be easily molded by the inkjet method.

Such a low viscosity of composition (X) can be achieved by appropriately adjusting the composition of radically polymerizable compound (A) within the range described above. The method and conditions for measuring the viscosity of composition (X) will be explained in detail in the Examples section below.

The rate of outgassing generated when the cured product of composition (X) is heated at 110°C for 30 minutes is preferably 25 ppm or less. In other words, by increasing the curability of composition (X) according to this embodiment, it is preferable that the rate of outgassing generated from the cured product is 25 ppm or less. In this case, outgassing is less likely to occur from the cured product. This makes it possible to make it difficult for voids due to outgassing to occur in a light-emitting device that includes an optical component made of the cured product, for example. This makes it difficult for water and oxygen to reach the light-emitting element through voids, making it difficult for the light-emitting element to deteriorate due to water and oxygen. It is particularly preferable for this rate of outgassing to be 15 ppm.

The reduction in the proportion of outgassing generated from the cured product of composition (X) can be achieved by appropriately adjusting the composition of radically polymerizable compound (A) within the range described above. The method for measuring the proportion of outgassing will be described in detail in the Examples below.

The glass transition temperature of the cured product of the composition (X) is preferably 75°C or higher. In other words, the composition (X) preferably has the property of curing to become a cured product with a glass transition temperature of 75°C or higher. In this case, the cured product can have good heat resistance. Therefore, for example, when the cured product is subjected to a process involving an increase in temperature, the cured product is less likely to deteriorate. Therefore, for example, when an inorganic film (e.g., passivation layer 6) that overlaps an optical component is produced by a deposition method such as a plasma CVD method, the optical component is less likely to deteriorate even if the optical component is heated. In addition, by increasing the heat resistance, the optical component can be adapted to applications such as vehicle-mounted applications that have strict requirements for heat resistance. The glass transition temperature of the cured product is more preferably 90°C or higher, even more preferably 110°C or higher, and particularly preferably 125°C or higher. This glass transition temperature of the cured product can be achieved by appropriately adjusting the composition of the radical polymerizable compound (A) within the range described above.

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

It is preferable that the dielectric constant of the cured product made from the composition is 3.8 or less when the measurement frequency is 100 kHz. In this case, when the cured product is applied to an optical component in a light-emitting device, the operational reliability of the light-emitting device can be improved. In particular, when the cured product is applied to an optical component in a light-emitting device equipped with a touch sensor, malfunction of the touch sensor can be suppressed. It is more preferable that the dielectric constant of the cured product is 3.4 or less, and even more preferable that it is 3.0 or less. This dielectric constant of the cured product can be achieved by appropriately adjusting the composition of composition (X) within the range described above.

4. Optical component and light-emitting device An example of the structure of a light-emitting device 1 including an optical component made from the composition (X) will be described. The light-emitting device 1 includes a light source and an optical component that transmits light emitted by the light source. For example, the light-emitting device 1 includes a light-emitting element 4, and a sealant 5 and a passivation layer 6 that cover the light-emitting element 4. In this case, the light-emitting element 4 is the light source, the sealant 5 is the optical component, and the passivation layer 6 is an inorganic film. The sealant 5 and the passivation layer 6 overlap each other.

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 is an abbreviation for electroluminescence.

An example of the structure of the light-emitting device 1 will be described with reference to FIG. 1. This light-emitting device 1 is a top-emission type. The light-emitting device 1 includes a support substrate 2, a transparent substrate 3 that faces the support substrate 2 with a gap therebetween, a light-emitting element 4 on the surface of the support substrate 2 that faces the transparent substrate 3, and a passivation layer 6 and a sealing material 5 that cover the light-emitting element 4.

The support substrate 2 is made of, for example, but not limited to, a resin material. The transparent substrate 3 is made of a light-transmitting material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate. The light-emitting element 4 includes, for example, a pair of electrodes 41, 43 and an organic light-emitting layer 42 between the electrodes 41, 43. The organic light-emitting layer 42 includes, for example, a hole injection layer 421, a hole transport layer 422, an organic light-emitting layer 423, and an electron transport layer 424, and these layers are stacked in the above order.

The light-emitting device 1 includes a plurality of light-emitting elements 4, which form an array 9 (hereinafter referred to as element array 9) on a support substrate 2. The element array 9 also includes a partition 7. The partition 7 is on the support substrate 2 and separates two adjacent light-emitting elements 4. The partition 7 is fabricated, for example, by forming a photosensitive resin material using a photolithography method. The element array 9 also includes connection wiring 8 that electrically connects the electrodes 43 and electron transport layers 424 of adjacent light-emitting elements 4. The connection wiring 8 is provided on the partition 7.

The passivation layer 6 corresponds to an inorganic film. The passivation layer 6 is preferably made of silicon nitride or silicon oxide, and is particularly preferably made of silicon nitride. In the example shown in FIG. 1, 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 being in direct contact with the element array 9, thereby covering the light-emitting element 4. The second passivation layer 62 is disposed on the opposite side of the element array 9 with respect to the first passivation layer 61, and a gap is provided between the second passivation layer 62 and the first passivation layer 61. The sealant 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 sealant 5 covering the light-emitting element 4.

Furthermore, a second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing material 52 is made of, for example, a transparent resin material. There are no particular limitations on the material of the second sealing material 52. The material of the second sealing material 52 may be the same as or different from the sealing material 5.

A method for producing the encapsulant 5 using composition (X) and a method for producing the light emitting device 1 are described.

In this embodiment, it is preferable to eject the composition (X) by an inkjet method to form a film, and then irradiate the composition (X) with ultraviolet light to harden it, thereby producing the sealing material 5. In this embodiment, the composition (X) can be ejected and shaped by an inkjet method.

When discharging the composition (X) by the inkjet method, if the composition (X) has a sufficiently low viscosity at room temperature, for example, if the viscosity at 25°C is 30 mPa·s or less, particularly 16 mPa·s or less, the composition (X) can be molded by discharging it by the inkjet method without heating it. If the viscosity of the composition (X) is reduced by heating, the composition (X) may be heated and then discharged by the inkjet method to be molded. As described above, if the viscosity of the composition (X) at 40°C is particularly 16 mPa·s or less, the viscosity of the composition (X) can be reduced by simply heating it slightly, and this reduced-viscosity composition (X) can be discharged by the 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. On one surface of the support substrate 2, partition walls 7 are fabricated by photolithography using, for example, a photosensitive resin material. Next, a plurality of light-emitting elements 4 are provided on one surface of the support substrate 2. The light-emitting elements 4 can be fabricated by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to fabricate the light-emitting elements 4 by a coating method such as an inkjet method. In this way, an element array 9 is fabricated on the support substrate 2.

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

Next, the composition (X) is ejected onto the first passivation layer 61, for example, by an inkjet method, and shaped to form a coating film. By applying the inkjet method to both the production of the light-emitting element 4 and the formation of the coating film, the production efficiency of the light-emitting device 1 can be particularly improved. Next, the coating film of the composition (X) is cured by irradiating it with light, to produce the encapsulant 5.

When irradiating composition (X) with light, composition (X) may be irradiated with light in an atmosphere containing oxygen, such as an air atmosphere, or composition (X) may be irradiated with light in an inert atmosphere, such as a nitrogen atmosphere.

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

Next, a photocurable resin material is applied to one surface of the support substrate 2 so as to cover the second passivation layer 62, and then the transparent substrate 3 is placed on top of this resin material. The transparent substrate 3 is, for example, a glass substrate or a transparent resin substrate.

Next, ultraviolet light is applied from the outside toward the transparent substrate 3. The ultraviolet light passes through the transparent substrate 3 and reaches the photocurable resin material. This causes the photocurable resin material to harden, producing the second sealing material 52.

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 even more preferably 15 μm or less. In this case, by thinning the sealing material 5, the light emitting device 1 can be thinned, and it is also possible to obtain a flexible light emitting device 1, i.e., a bendable light emitting device. In order to effectively suppress moisture from entering the light emitting element 4 by the sealing material 5, the thickness of the sealing material 5 is preferably 3 μm or more, more preferably 5 μm or more, and even more preferably 8 μm or more.

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. When the passivation layer 6 includes the first passivation layer 61 and the second passivation layer 62 as described above, it is preferable that the thickness of each of the first passivation layer 61 and the second passivation layer 62 is 0.1 μm or more and 2 μm or less.

The light-emitting device 1 may be a deformable light-emitting device 1 such as a foldable display. In the embodiment, the sealing material 5 is flexible and has high adhesion to the passivation layer 6, which is an inorganic film, so that even if the light-emitting device 1 is bent or otherwise deformed, damage to the sealing material 5 can be suppressed.

The light emitting device may be equipped with a touch sensor. In this embodiment, the relative dielectric constant of the sealing material 5 can be reduced, which can prevent the touch sensor from malfunctioning.

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

According to this embodiment, the flexibility of the cured product of the composition containing the silicon-containing acrylic compound (a) can be increased.

In the second embodiment, the organic group (g) in the first embodiment has a cycloalkane skeleton.

According to this embodiment, the flexibility of the cured product of the composition containing the silicon-containing acrylic compound (a) can be further increased.

In the third embodiment, a (meth)acryloyl group is bonded to the cycloalkane skeleton in the organic group (g) via an oxygen atom in the second embodiment.

In a fourth embodiment, in any one of the first to third embodiments, the silicon-containing acrylic compound (a) has multiple (meth)acryloyl groups in the molecule.

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

In the fifth embodiment, the number of (meth)acryloyl groups in the molecule is 2 or more and 4 or less in the fourth embodiment.

In this embodiment, the glass transition temperature of the cured product of the silicon-containing acrylic compound (a) and the composition containing the silicon-containing acrylic compound (a) can be increased while suppressing an increase in viscosity.

The photocurable resin composition according to the sixth aspect contains a radically polymerizable compound (A), and the radically polymerizable compound (A) contains the silicon-containing acrylic compound (a) according to any one of the first to fifth aspects as a first radically polymerizable compound.

In this embodiment, the silicon-containing acrylic compound (a) can increase the flexibility of the cured product of the photocurable resin composition.

In a seventh embodiment, the photocurable resin composition of the sixth embodiment further contains a photoradical polymerization initiator (B).

In the eighth embodiment, the radical polymerizable compound (A) in the sixth or seventh embodiment further contains a monofunctional radical polymerizable compound (b) having a nitrogen atom in the molecule as a second radical polymerizable compound.

This embodiment can improve the adhesion of the cured product of the photocurable resin composition to inorganic materials.

In a ninth aspect, in any one of the sixth to eighth aspects, the radically polymerizable compound (A) further contains an acrylic compound (c) having a chain-like saturated hydrocarbon skeleton with 5 to 25 carbon atoms in the molecule and a (meth)acryloyl group as a third radically polymerizable compound.

According to this embodiment, the dielectric constant of the cured product of the photocurable resin composition can be reduced.

In a tenth aspect, in any one of the sixth to ninth aspects, the viscosity of the photocurable resin composition at 25°C is 50 mPa·s or less.

In this embodiment, the photocurable resin composition has good moldability, and it may be possible to mold it by ejecting it using the inkjet method.

The optical component according to the eleventh aspect includes a cured product of the photocurable resin composition according to any one of the sixth to tenth aspects.

This embodiment increases the flexibility of the optical components, and can prevent damage to the optical components during deformation.

The method for producing an optical component according to the twelfth aspect includes ejecting the photocurable resin composition according to any one of the sixth to tenth aspects by an inkjet method, and then irradiating the photocurable resin composition with light to cure it.

This method allows optical components to be manufactured with high positional accuracy and reduces the yield.

The light-emitting device (1) according to the thirteenth aspect includes a light source and an optical component that transmits light emitted by the light source, and the optical component includes a cured product of the photocurable resin composition according to any one of the sixth to tenth aspects.

This embodiment increases the flexibility of the optical components, and can prevent damage to the optical components when they are deformed.

The manufacturing method for the light-emitting device (1) according to the fourteenth aspect 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 manufacturing the optical component by the method according to the twelfth aspect.

According to this embodiment, the optical components in the light emitting device (1) can be manufactured with high positional precision, and the yield is less likely to deteriorate.

1. Synthesis of silicon-containing acrylic compound (1) Synthesis Example 1
First, 300 parts (1.5 equivalent parts) of Shin-Etsu Chemical Co., Ltd.'s KR470 (epoxy equivalent 200 g/mol) and 258 parts (3 equivalent parts) of methacrylic acid (molecular weight 86 g/mol) were added to a four-neck flask equipped with a stirring blade/device, a cooling tube, and a thermometer, and the mixture was homogenized by stirring. Next, 2.0 parts of triphenylphosphine, 0.2 parts of hydroquinone monomethyl ether, and 2.0 parts of phenolsulfonic acid were added and mixed to dissolve the solid content. The liquid temperature was raised to 80°C to 90°C, and the mixture was allowed to react for 10 hours at a temperature range of 80°C to 90°C. As a result, a compound having the structure shown in formula (4) was synthesized.

The compound obtained by the above synthesis was analyzed by an infrared spectrometer (FTIR), and it was confirmed that there was no peak (902 cm ⁻¹ ) derived from an epoxy group, but a peak (1731 cm ⁻¹ ) derived from C═O was generated. This confirmed that the compound obtained by the above synthesis had a structure represented by formula (4).

(2) Synthesis Example 2
Instead of KR470 manufactured by Shin-Etsu Chemical Co., Ltd., 435 parts (1.5 equivalent parts) of X-22-2678 (epoxy equivalent weight 290 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used. Except for this, a compound having a structure shown in formula (3) was synthesized in the same manner as in Synthesis Example 1.

(3) Synthesis Example 3
Instead of product number KR470 manufactured by Shin-Etsu Chemical Co., Ltd., 300 parts (1.5 equivalent parts) of product number X-40-2728 (epoxy equivalent weight 200 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used. Except for this, a silicon-containing acrylic compound having a cyclic siloxane skeleton and four methacryloyl groups in the molecule and no cycloalkane skeleton was synthesized in the same manner as in Synthesis Example 1.

(4) Synthesis Example 4
Instead of product number KR470 manufactured by Shin-Etsu Chemical Co., Ltd., 420 parts (1.5 equivalent parts) of product number X-40-2669 (epoxy equivalent weight 280 g/mol) manufactured by Shin-Etsu Chemical Co., Ltd. was used. Except for this, a silicon-containing acrylic compound having a linear siloxane skeleton and four methacryloyl groups in the molecule and no cycloalkane skeleton was synthesized in the same manner as in Synthesis Example 1.

2. Preparation of Compositions 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 as follows.
Silicon-containing acrylic compound #1: a compound having a structure shown in formula (11), synthesized in Synthesis Example 1.
Silicon-containing acrylic compound #2: a compound having a structure shown in formula (12), synthesized in Synthesis Example 2.
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, but does not have a cycloalkane skeleton.
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, but does not have a cycloalkane skeleton.
Silicon-containing acrylic compound #5: Dimethyl silicone methacrylate, product number X-22-164A from Shin-Etsu Chemical Co., Ltd.
-N-containing monofunctional compound #1: Vinylmethyloxazolidinone, manufactured by BASF, product name VMOX.
-N-containing monofunctional compound #2: acryloylmorpholine, manufactured by KJ Chemicals Co., Ltd. Product name: ACMO.
-N-containing monofunctional compound #3: N,N-dimethylacrylamide. Manufactured by KJ Chemicals Co., Ltd. Product name: DMAA.
- Acrylic compound #1: 1,12-dodecanediol dimethacrylate. Manufactured by Sartomer. Product name: SR262.
- Acrylic compound #2: 1,9-nonanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. Product name: Viscoat #260.
- Acrylic compound #3: Isostearyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. Product name: ISTA.
- Acrylic compound #4: Cetyl acrylate, manufactured by NOF Corporation, product name: Blenmar CA.
- Acrylic compound #5: Tripropylene glycol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. Product name: Viscoat #310HP.
Acrylic compound #6: A compound represented by the following chemical formula (8), manufactured by Kyoeisha Chemical Co., Ltd. Product name: Light Acrylate NMT-A.

Photo-radical polymerization initiator: acylphosphine oxide-based photo-polymerization initiator, manufactured by IGM Resins B.V. Product name: Omnirad TPO H.
- Antioxidant: BASF product name: Irganox 1010.
-Leveling agent: BYK-Chemie. Product name: BYK330.

3. Evaluation Test (1) Dielectric Constant A coating film of the composition having a thickness of 10 μm was prepared on an aluminum substrate having dimensions of 80 mm×40 mm×1 mmt. The coating film was irradiated with ultraviolet light for 15 seconds under the condition of 100 mW/ ^cm2 to cure the coating film. The dielectric constant of the cured coating film was measured by the electrode contact method using an LCR meter (manufactured by Agilent, "E4980A") and a jig (16034 test fixture) under the condition of a measurement frequency of 100 kHz.

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

(3) Inkjet properties The composition was placed in a cartridge of an inkjet printer (manufactured by Fujifilm, model DMP2831), and droplets of the composition were ejected from the nozzle of the inkjet printer under conditions of a temperature of 40° C. and a frequency of 1 kHz. The droplets were observed with a high-speed camera. As a result, the following evaluation was performed: when the droplets did not separate, it was rated as "A"; when the satellites separated from the original droplets and then merged with the original droplets to form one droplet again, it was rated as "B"; and when the satellites separated from the original droplets and did not merge, it was rated as "C."

(4) Curability The composition was measured with an infrared spectrometer (Agilent Cary 610 FTIR Microscope System, manufactured by Agilent Technologies) to obtain an IR spectrum.

The composition was applied to prepare a coating film having a thickness of 10 μm, and the coating film was irradiated with light having a peak wavelength of 395 nm under a nitrogen atmosphere using a UV irradiator (manufactured by Ushio Inc., model number Unijet E075IIHD) under conditions of an irradiation intensity of 0.5 W/cm ² and an integrated light quantity of 1.5 J/cm ^2. The composition (cured product) after irradiation with ultraviolet light was then measured with the above-mentioned infrared spectrometer to obtain an IR spectrum.

In each of the two IR spectra, the peak intensity of the absorption of the acryloyl group appearing at 810 cm ^-1 was measured. From the peak intensity I ₀ for the coating film and the peak intensity I ₁ for the cured product, the reduction rate of the reactive functional group in the composition before and after irradiation with ultraviolet light was calculated using the formula {1-(I ₀ -I ₁ )/I ₀ }×100(%). The result was taken as the reaction rate, and the reaction rate was evaluated as "A" when it was 90% or more, "B" when it was 80% or more but less than 90%, and "C" when it was less than 80%.

(5) Outgassing Evaluation The outgassing when the cured product of the composition was heated was sampled by the headspace method and measured by gas chromatography. In detail, 100 mg of the composition was first placed in a headspace vial with a volume of 22 mL. Next, the composition was cured by irradiating the composition with light having a peak wavelength of 395 nm under a nitrogen atmosphere using a UV irradiator (manufactured by Ushio Electric, model number Unijet E075IIHD) under conditions of an irradiation intensity of 0.5 W/cm ² and an accumulated light amount of 1.5 J/cm ² , and then the vial was sealed. Next, the composition was heated at 110°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 concentration of the outgassing generated from the composition was specified based on the peak area of the obtained gas chromatogram. The concentration of the outgassing is the volume fraction of the outgassing in the gas phase of the vial relative to the volume of the vial (22 mL).

The outgassing concentration was determined using toluene as the standard substance. Specifically, two standard samples with toluene concentrations of 1000 ppm and 100 ppm were prepared by volatilizing toluene in a vial. Each standard sample was introduced into a gas chromatograph for analysis. From the peak areas of the two chromatograms obtained in this way, the relationship between peak area and concentration was determined, and the above-mentioned outgassing concentration was determined based on these results.

(6) Adhesion A silicon oxynitride film (SiON film), which is an inorganic film, was formed on a slide glass by CVD to a thickness of 1 μm. A coating film was formed by applying a composition to a thickness of 10 μm on this inorganic film, and this coating film was irradiated with light having a peak wavelength of 395 nm under a nitrogen atmosphere using a UV irradiator (manufactured by Ushio Electric, model number Unijet E075IIHD) under conditions of an irradiation intensity of 0.5 W/cm ² and an accumulated light quantity of 1.5 J/cm ^2. This coating film was pulled in the 90 degree direction with an autograph (manufactured by Shimadzu Corporation, model number AGS-X) to measure the peel strength. A peel strength of 100 mN/cm or more was rated as "A", a peel strength of 50 mN/cm or more was rated as "B", a peel strength of 20 mN/cm or more was rated as "C", and a peel strength of less than 20 mN/cm was rated as "D".

(7) Flexibility A silicon oxynitride film (SiON film), which is an inorganic film, was formed to a thickness of 1 μm on a polyimide film, which is a substrate, by a CVD method. The composition was applied to the inorganic film to a thickness of 10 μm to form a coating film, and the coating film was irradiated with light having a peak wavelength of 395 nm under a nitrogen atmosphere using a UV irradiator (manufactured by Ushio Electric, model number Unijet E075IIHD) under conditions of an irradiation intensity of 0.5 W/cm ² and an accumulated light amount of 1.5 J/cm ² to produce a film having a thickness of 10 μm. As a result, an evaluation sample including a substrate, an inorganic film, and a film was produced.

This evaluation sample was subjected to a test in which it was repeatedly bent 100,000 times under conditions in which the radius of curvature of the bent portion was 1.5 mm, 2.0 mm, and 3.0 mm.

As a result, the test was rated as follows: if no peeling or cracking was observed on the exterior after 100,000 tests with a radius of curvature of 1.5 mm, it was rated as "A"; if no peeling or cracking was observed with a radius of 2.0 mm but was observed with a radius of 1.5 mm, it was rated as "B"; if no peeling or cracking was observed with a radius of 3.0 mm but was observed with a radius of 2.0 mm, it was rated as "C"; and if peeling or cracking was observed with a radius of 3.0 mm, it was rated as "D".

(9) Glass transition temperature A coating film was prepared by applying the composition, and the coating film was photocured by irradiating the coating film under atmospheric conditions with light having a peak wavelength of 395 nm using a UV irradiator (manufactured by Ushio Inc., model number E075IIHD) under conditions of an irradiation intensity of 3 W/ ^cm2 and an accumulated light quantity of 15 J/ ^cm2 , thereby preparing a film having a thickness of 500 μm. The glass transition temperature of a sample cut out from the film was measured using a viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Corporation, model number DMA7100).

1 Light emitting device 4 Light emitting element (light source)
5. Sealing material (optical parts)

Claims

In the molecule,
A cyclic siloxane skeleton;
an organic group having a (meth)acryloyl group bonded to the cyclic siloxane skeleton;
having
Silicon-containing acrylic compounds.
The organic group has a cycloalkane skeleton.
The silicon-containing acrylic compound according to claim 1 .
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 2 .
A compound having a plurality of (meth)acryloyl groups including the (meth)acryloyl group in a molecule.
The silicon-containing acrylic compound according to claim 1 .
the number of (meth)acryloyl groups in the molecule is 2 or more and 4 or less;
The silicon-containing acrylic compound according to claim 4 .
Contains a radically polymerizable compound (A),
The radical polymerizable compound (A) contains the silicon-containing acrylic compound according to any one of claims 1 to 5 as a first radical polymerizable compound;
Photocurable resin composition.
Further containing a photoradical polymerization initiator (B),
The photocurable resin composition according to claim 6.
The radical polymerizable compound (A) further contains a monofunctional radical polymerizable compound having a nitrogen atom in the molecule as a second radical polymerizable compound.
The photocurable resin composition according to claim 6.
the radical polymerizable compound (A) further contains, as a third radical polymerizable compound, an acrylic compound having a chain-like saturated hydrocarbon skeleton having 5 to 25 carbon atoms in the molecule and a (meth)acryloyl group;
The photocurable resin composition according to claim 6.
The viscosity at 25°C is 50 mPa·s or less.
The photocurable resin composition according to claim 6.
The cured product of the photocurable resin composition according to claim 6 is included.
Optical components.
The photocurable resin composition according to claim 6 is ejected by an inkjet method, and then the photocurable resin composition is irradiated with light to be cured.
A method for manufacturing optical components.
A light source and an optical component that transmits light emitted by the light source, the optical component including a cured product of the photocurable resin composition according to claim 6.
Light emitting device.
A method for manufacturing a light emitting device including a light source and an optical component that transmits light emitted by the light source, comprising the steps of:
The optical component is manufactured by the method of claim 12.
A method for manufacturing a light emitting device.