JP2022142675A - Photocurable resin composition, optical component, method for producing optical component, light-emitting device, and method for producing light-emitting device - Google Patents

Abstract

To provide a photocurable resin composition that retains its curability and has excellent storageability while containing an ultraviolet absorber.SOLUTION: A photocurable resin composition contains a photopolymerizable compound (A), a photopolymerization initiator (B), an ultraviolet absorber (C), and a sensitizer (D). The photopolymerizable compound (A) contains a monofunctional photopolymerizable compound (A011). The percentage of the monofunctional photopolymerizable compound (A011) relative to the solid content is 10 mass% or more and 40 mass% or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photocurable resin composition, an optical component, a method for producing an optical component, a light-emitting device, and a method for producing a light-emitting device, and more particularly to a photocurable resin containing a photopolymerizable compound and a photopolymerization initiator. A composition, 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 comprising the optical component, and using the photocurable resin composition The present invention relates to a method for manufacturing a light emitting device.

In a light-emitting device including a light-emitting element such as an organic EL element as a light source, for example, an organic EL element is arranged on a supporting substrate, a transparent substrate is arranged so as to face the supporting substrate, and a transparent substrate is arranged between the supporting substrate and the transparent substrate. is filled with a suitable encapsulant. The sealing material is produced, for example, by an inkjet method.

For example, Patent Document 1 discloses a sealant for an organic EL display device containing a polymerizable compound, wherein the polymerizable compound has a surface tension of 35 mN/m or more at 25°C in 100 parts by weight of the polymerizable compound. 30 parts by weight or more, the viscosity of the entire sealant for organic EL display elements at 25 ° C. is 5 mPa s or more and 50 mPa s or less, and the surface tension of the entire sealant for organic EL display elements at 25 ° C. is A sealant for an organic EL display device having a density of 35 mN/m or less is disclosed.

WO2018/131553

According to research conducted by the inventors, when a light-emitting device is used outdoors, deterioration of light sources such as light-emitting elements tends to progress more easily than when it is used indoors.

Therefore, the inventor conducted his own research in order to suppress the deterioration of the light source, and tried to prevent the ultraviolet rays from reaching the light source by incorporating an ultraviolet absorber into the optical parts of the light-emitting device. .

However, the inventor believes that the use of a UV absorber makes it difficult to cure the photocurable material because the UV absorber absorbs light when an optical component is to be made from a photocurable material. . In addition, the inventors have found that if a sensitizer is used to enhance the curability of a photocurable material, the reaction of the photocurable material progresses during storage, resulting in an increase in viscosity. Found it.

An object of the present invention is to provide a photocurable resin composition that contains an ultraviolet absorber, does not easily deteriorate in curability, and has good storage stability, and an optical product made from the photocurable resin composition. An object of the present invention is to provide a component, 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 a light-emitting device using the photocurable resin composition.

The photocurable resin composition according to one aspect of the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), an ultraviolet absorber (C), and a sensitizer (D). The photopolymerizable compound (A) contains a monofunctional photopolymerizable compound (A011), and the percentage of the monofunctional photopolymerizable compound (A011) to the solid content is 10% by mass or more and 40% by mass or less. is.

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

A method for manufacturing an optical component according to an aspect of the present invention includes forming the photocurable resin composition by an inkjet method and then curing the photocurable resin composition by irradiating light.

A light-emitting device according to an aspect of the present invention 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 an aspect of the present invention 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 the optical component is a method for manufacturing the optical component. including manufactured in

According to one aspect of the present invention, a photocurable resin composition that contains an ultraviolet absorber, is less likely to deteriorate in curability, and can have good storage stability, is produced 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 a light-emitting device using the photocurable resin composition.

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

An embodiment of the present invention will be described below.

The photocurable resin composition (hereinafter also referred to as composition (X)) according to the present embodiment includes a photopolymerizable compound (A), a photopolymerization initiator (B), an ultraviolet absorber (C), and a sensitizer (D). The photopolymerizable compound (A) contains a monofunctional photopolymerizable compound (A011). The percentage ratio of the monofunctional photopolymerizable compound (A011) to the solid content in the composition (X) is 10% by mass or more and 40% by mass or less.

According to this embodiment, a cured product can be produced by irradiating the composition (X) with light. Although the composition (X) contains the ultraviolet absorber (C), it further contains the sensitizer (D), so that good reactivity is maintained when the composition (X) is irradiated with light. Cheap. In addition, since ultraviolet rays are absorbed by the ultraviolet absorber (C), it is difficult for the cured product to transmit ultraviolet rays. Further, since the photopolymerizable compound (A) contains the monofunctional photopolymerizable compound (A011), even if the polymerization reaction of the monofunctional photopolymerizable compound (A011) proceeds somewhat, the viscosity of the composition (X) is Since it does not fluctuate greatly, it is possible to suppress the increase in viscosity of composition (X) during storage of composition (X), that is, it is easy to improve the storage stability of composition (X). Especially in this embodiment, since the composition (X) contains the sensitizer (D), the reaction of the photopolymerizable compound (A) is promoted by the sensitizer (D) during storage of the composition (X). However, even in such a case, the monofunctional photopolymerizable compound (A011) makes it difficult for the composition (X) to increase in viscosity. Since the percentage of the monofunctional photopolymerizable compound (A011) to the solid content in the composition (X) is 10% by mass or more, the storage stability of the composition (X) is likely to increase, and this percentage is 40% by mass or less. Therefore, the reactivity of the composition (X) is easily ensured.

As a result, in the present embodiment, the composition (X) that contains the ultraviolet absorber, does not easily deteriorate in curability, and can have good storability can be obtained.

In the present embodiment, it is preferable that the transmittance of light having a wavelength of 400 nm of a 10 μm-thick cured product obtained by curing the composition (X) is 30% or less. In this case, the cured product becomes particularly difficult to transmit ultraviolet rays. This transmittance is more preferably 20% or less, and even more preferably 10% or less. This transmittance is preferably as low as possible, ideally 0%. This low transmittance can be achieved by selecting the UV absorber (C) and the sensitizer (D).

In the present embodiment, the transmittance of light having a wavelength of 430 nm in a 10 μm-thick cured product obtained by curing the composition (X) is preferably 70% or more. In this case, the cured product hardly inhibits the transmission of visible light. Therefore, when the composition (X) is used to produce an optical component in a light-emitting device, the light-emitting performance of the light-emitting device is less likely to be impaired by the optical component. This transmittance is preferably 80% or more, more preferably 90% or more. This transmittance can be achieved by selecting the UV absorber (C) and the sensitizer (D).

In the present embodiment, the composition (X) is preferably curable when irradiated with light having a peak wavelength of 395 nm. In particular, in the present embodiment, a coating film having a thickness of 10 μm is prepared from the composition (X), and the coating film is irradiated with light having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light amount of 0.9 J/cm ² . The reaction rate of the photopolymerizable compound (A) in the composition (X) when irradiated is preferably 80% or more. In this case, although the composition (X) contains the ultraviolet absorber (C), the composition (X) can be cured using ultraviolet rays having a wavelength of around 395 nm. Such properties can be achieved by selection of the sensitizer (D). This reaction rate is more preferably 90% or more.

These properties of composition (X) and the cured product can be realized by the composition of composition (X) described in detail below.

An optical component can be produced from the composition (X), and a light-emitting device comprising the optical component can also be produced. The application of the composition (X) is not limited to the production of optical parts, and can be applied to various applications utilizing the characteristics of the composition (X).

Composition (X) is preferably molded by an inkjet method. In this case, the cured product of the composition (X) and the optical component can be easily produced with high positional accuracy. In addition, when the composition (X) is molded by an inkjet method, foreign matter is less likely to be mixed into the composition (X) and its cured product, compared with the case where the composition (X) is molded by a printing method involving contact such as a screen printing method. Therefore, the yield in manufacturing optical components is less likely to deteriorate.

In the present embodiment, it is preferable that the composition (X) has a viscosity at 25° C. of 30 mPa·s or less. In this case, the composition (X) is easily molded, particularly by an inkjet method. This viscosity is more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity is preferably 1 mPa·s or more, more preferably 5 mPa·s or more.

It is also preferable that the composition (X) has a viscosity at 40° C. of 30 mPa·s or less. In this case, even if the viscosity of the composition (X) at room temperature is any value, the viscosity of the composition (X) can be lowered by slightly heating the composition (X). Therefore, by heating, the composition (X) can be easily molded, particularly by an inkjet method. Moreover, since the viscosity of the composition (X) can be lowered without significantly heating the composition (X), changes in the composition of the composition (X) due to volatilization of the components in the composition (X) can be suppressed. This viscosity is more preferably 25 mPa·s or less, further preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity is preferably 1 mPa·s or more, more preferably 5 mPa·s or more.

Such a low viscosity of composition (X) at 25° C. or 40° C. can be achieved by the composition of composition (X) described in detail below. The method and conditions for measuring the viscosity of composition (X) at 25° C. and 40° C. will be described in detail in the Examples section below.

It is preferable that the proportion of outgas generated when the cured product of composition (X) is heated at 100° C. for 30 minutes is 300 ppm or less. In this case, outgassing is less likely to occur from the cured product. Therefore, for example, voids due to outgassing are less likely to occur in a light-emitting device including an optical component made of a cured product. Therefore, water and oxygen are less likely to reach the light-emitting element through the gap, and the light-emitting element is less likely to be deteriorated by water and oxygen. More preferably, the outgas ratio is 100 ppm or less. A method for measuring the outgassing ratio will be described in detail in the examples given later.

The composition (X) preferably contains no solvent or a solvent content of 1% by mass or less. In this case, the composition (X) and the cured product of the composition (X) are less likely to generate outgassing derived from the solvent. In addition, a drying process for removing the solvent from the composition (X) and the cured product can be eliminated during the production of optical parts and light-emitting devices. There may be a drying step for removing the solvent from at least one of the composition (X) and the cured product. In this case, at least one of reducing the heating temperature and shortening the heating time in the drying step is possible. can be done. Therefore, outgassing from the optical components can be suppressed without lowering the manufacturing efficiency of the optical components and the light-emitting device. Furthermore, when the composition (X) is molded particularly by an inkjet method, the thickness of the composition (X) is less likely to decrease due to volatilization of the solvent from the molded composition (X), and therefore the thickness of the optical component is less likely to decrease. Therefore, the thickness of the optical component can be ensured as large as possible while being molded by the inkjet method. The solvent content is more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferred that the composition (X) contains no solvent or only unavoidably mixed solvents.

The cured product of composition (X) preferably has a glass transition temperature of 75° C. or higher. That is, the composition (X) preferably has the property of being cured to a cured product having 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 treatment that involves a temperature rise, the cured product is less likely to deteriorate. Therefore, when a layer of an inorganic material (for example, the passivation layer 6) overlaid on 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 in-vehicle applications that require strict heat resistance. The glass transition temperature of the cured product is preferably 80° C. or higher, more preferably 90° C. or higher, and particularly preferably 100° C. or higher. The glass transition temperature of this cured product can be achieved by the composition of composition (X) described in detail below.

The volatility when 20 mg of composition (X) is heated at 100° C. for 30 minutes using a thermogravimetric analyzer is preferably 40% or less. The volatility of composition (X) is the weight loss of composition (X) after treatment relative to the weight of composition (X) before treatment (the weight of composition (X) before treatment and after treatment weight difference) is defined as a percentage. In this case, the low volatility of the composition (X) can improve the storage stability of the composition (X). In addition, outgassing is less likely to occur from the cured product of the composition (X) and optical parts. Therefore, voids due to outgassing are less likely to occur in the light-emitting device. The volatility of the composition (X) was measured by heating 20 mg of the composition (X) at 100° C. for 30 minutes using a thermogravimetric analyzer, and calculating the weight loss after the treatment relative to the weight before the treatment. can be obtained by calculating The volatility when 20 mg of composition (X) is heated at 100° C. for 30 minutes using a thermogravimetric analyzer is more preferably 30% or less, more preferably 20% or less. preferable. Although the lower limit of volatility of composition (X) is not particularly limited, it may be, for example, 0.1% or more.

The components contained in composition (X) are described in more detail.

The photopolymerizable compound (A) and the photopolymerization initiator (B) will be explained.

The photopolymerizable compound (A) is a compound capable of undergoing a polymerization reaction upon irradiation with light. The photopolymerizable compound (A) contains, for example, at least one component selected from the group consisting of monomers, oligomers and prepolymers.

As described above, the photopolymerizable compound (A) contains a monofunctional photopolymerizable compound (A011) having only one polymerizable functional group, and a monofunctional photopolymerizable compound (A011) with respect to the solid content in the composition (X). The percentage of compound (A011) is 10% by mass or more and 40% by mass or less. When this percentage is 10% by mass or more, the storage stability of composition (X) is likely to be enhanced. Further, when this percentage is 40% by mass or less, the reactivity of the composition (X) is more likely to be ensured. This percentage is more preferably 12% by mass or more, and even more preferably 14% by mass or more. This percentage is more preferably 30% by mass or less, and even more preferably 20% by mass or less.

The photopolymerizable compound (A) may further contain a polyfunctional photopolymerizable compound (A012) having two or more polymerizable functional groups. In this case, the reactivity of the composition (X) is increased when the composition (X) is irradiated with light. Therefore, good reactivity can be achieved when the composition (X) is irradiated with light having a wavelength of about 395 nm, and outgassing from the cured product is suppressed.

The percentage ratio of the polyfunctional photopolymerizable compound (A012) to the solid content in the composition (X) is preferably 50% by mass or more. In this case, the reactivity of the composition (X) is more likely to be ensured, and outgassing is less likely to occur. This percentage is more preferably 60% by mass or more, and even more preferably 70% by mass or more. Also, this percentage is preferably 90% by mass or less. In that case, there is an advantage that the viscosity increase of the composition (X) can be suppressed during storage of the composition (X), that is, the storage stability of the composition (X) can be easily improved. In addition, there is also the advantage that curing shrinkage can be sufficiently suppressed. This percentage is more preferably 85% by mass or less, and even more preferably 80% by mass or less.

The photopolymerizable compound (A) preferably contains a compound (A02) having at least one of -RO- skeleton and -RN- skeleton. In this case, bleeding out of the ultraviolet absorber (C) and the sensitizer (D) from the cured product is less likely to occur. It is presumed that this is because the affinity between the photopolymerizable compound (A) and the ultraviolet absorber (C) and the sensitizer (D) increases. R in each of the -RO- skeleton and the -RN- skeleton is a divalent hydrocarbon group such as an alkylene group having 2 or more carbon atoms. If the number of carbon atoms in R is 3 or more, higher effects are likely to be obtained. Moreover, the carbon number of R is, for example, 12 or less. However, from each of the -RO- skeleton and -RN- skeleton, the -RO- skeleton and -RN- skeleton present in the three-membered ring, and the -R-O- and -RN- skeletons are excluded.

The percentage ratio of compound (A02) to the solid content in composition (X) is preferably 10% by mass or more and 90% by mass or less. If this percentage is 10% by mass or more, bleeding out is even less likely to occur. When this percentage is 90% by mass or less, the storage stability of the composition (X) tends to be enhanced. This percentage is more preferably 30% by mass or more, and even more preferably 50% by mass or more. Moreover, it is more preferable if this percentage is 80% by mass or less.

The compound (A02) includes at least one of the -RO- skeleton and -RN- skeleton of the compounds described as specific examples of the compound contained in the photopolymerizable compound (A) described later. at least one compound selected from the group consisting of compounds having

The photopolymerizable compound (A) contains, for example, at least one of a radically polymerizable compound (A1) and a cationically polymerizable compound (A2). When the photopolymerizable compound (A) contains the radical polymerizable compound (A1), the photopolymerization initiator (B) preferably contains the radical photopolymerization initiator (B1). When the photopolymerizable compound (A) contains the cationic polymerizable compound (A2), the photopolymerization initiator (B) preferably contains the photocationic polymerization initiator (B2) (cationic curing catalyst).

A case where the photopolymerizable compound (A) contains the radically polymerizable compound (A1) will be described.

The radically polymerizable compound (A1) contains at least one of an acrylic compound (Y) and a radically polymerizable compound (Z) other than the acrylic compound (Y). The radically polymerizable compound (A1) preferably contains an acrylic compound (Y). Acrylic compound (Y) is a compound having one or more (meth)acryloyl groups in one molecule.

The viscosity of the entire acrylic compound (Y) at 25° C. is preferably 50 mPa·s or less. In this case, the acrylic compound (Y) can particularly lower the viscosity of the composition (X). The viscosity of the acrylic compound (Y) as a whole is more preferably 30 mPa·s or less, and particularly preferably 20 mPa·s or less. Further, the viscosity of the acrylic compound (Y) as a whole is, for example, 3 mPa·s or more.

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

The percentage of components having a boiling point of 270° C. or higher in the acrylic compound (Y) is preferably 80% by mass or higher. In this case, the storage stability of the composition (X) is particularly unlikely to be impaired, and outgassing is particularly unlikely to occur from the cured product. More preferably, the percentage of components having a boiling point of 280° C. or higher in the acrylic compound (Y) is 80 mass % or higher.

The acrylic compound (Y) preferably contains a component having a viscosity of 20 mPa·s or less at 25°C. In this case, the viscosity of composition (X) can be lowered.

The ratio of the component having a viscosity of 20 mPa·s or less at 25° C. to the total amount of the acrylic compound (Y) is preferably 50% by mass or more and 100% by mass or less. In this case, the viscosity of the composition (X) can be particularly lowered, making it particularly easy to apply the composition (X) by an inkjet method. This proportion is more preferably 60% by mass or more, and even more preferably 70% by mass or more. Further, this ratio is more preferably 95% by mass or less, and even more preferably 90% by mass or less.

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

A compound that the acrylic compound (Y) may contain will be described.

The acrylic compound (Y) includes a monofunctional acrylic compound (Y2) having only one (meth)acryloyl group as a radically polymerizable functional group in one molecule, and two or more containing (meth)acryloyl groups in one molecule. and at least one of the polyfunctional acrylic compound (Y1) having a radically polymerizable functional group. The monofunctional acrylic compound (Y2) is included in the aforementioned monofunctional photopolymerizable compound (A011), and the polyfunctional acrylic compound (Y1) is included in the aforementioned polyfunctional photopolymerizable compound (A012).

The polyfunctional acrylic compound (Y1) can increase the glass transition temperature of the cured product, and therefore can increase the heat resistance of the cured product. The proportion of the polyfunctional acrylic compound (Y1) is preferably 50% by mass or more and 100% by mass or less with respect to the entire acrylic compound (Y).

The polyfunctional acrylic compound (Y1) includes, for example, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol oligoacrylate, diethylene glycol diacrylate, 1,6-hexanediol oligoacrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentaerythritol tetraacrylate , propoxylation (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylation (3) trimethylolpropane triacrylate, propoxylation (3 ) glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, hexanediol diacrylate, polyethylene Glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate , 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol hydroxypivalate 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 lylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di( It contains at least one compound selected from the group consisting of meth)acrylates, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and 2-(2-vinyloxyethoxy)ethyl acrylate.

The acrylic equivalent of the polyfunctional acrylic compound (Y1) is preferably 150 g/eq or less, more preferably 90 g/eq or more and 150 g/eq or less. The weight average molecular weight of the polyfunctional acrylic compound (Y1) is, for example, 100 or more and 1000 or less, more preferably 200 or more and 800 or less.

The polyfunctional acrylic compound (Y1) preferably contains a compound (Y11) having a structure represented by formula (200) below.

_CH2 =CR1 ^- COO-(R3 ^- O)n-CO-CR2= ^CH2 ( ₂₀₀ )
In formula (200), each of R ¹ and R ² is hydrogen or a methyl group, n is an integer of 1 or more, R ³ is an alkylene group having 1 or more carbon atoms, and when n is 2 or more, A plurality of R ³ may be the same or different from each other.

When the number of carbon atoms in R ³ is 2 or more, compound (Y11) is included in compound (A02) above. R ³ is preferably an alkylene group having 3 to 6 carbon atoms.

Since compound (Y11) has the structure represented by formula (200), particularly because R ³ in formula (200) has 3 or more carbon atoms, it is difficult to increase the affinity of the cured product with water. The carbon number of R ³ is, for example, 1 or more and 15 or less, preferably 3 or more and 15 or less. In addition, the compound (Y11) has a structure represented by formula (200), particularly two (meth)acryloyl groups in one molecule, so that the glass transition temperature of the cured product can be increased. , the heat resistance of the cured product can be enhanced. Also, n in formula (200) is an integer of 1 or more and 12 or less, for example.

Compound (Y11) preferably contains a component having a boiling point of 270° C. or higher. That is, the acrylic compound (Y) preferably contains a component having a structure represented by formula (200) and a boiling point of 270° C. or higher. In this case, the acrylic compound (Y) is less likely to volatilize from the composition (X) during storage and when the composition (X) is heated. Therefore, the storage stability of composition (X) is less likely to be impaired. Further, even if the compound (Y11) remains unreacted in the cured product of the composition (X), outgassing due to the compound (Y11) is less likely to occur from the cured product. Therefore, voids due to outgassing are less likely to occur in the light emitting device 1 . If there is a gap in the light-emitting device 1, moisture may enter the light-emitting element 4 through the gap. The boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and can be determined, for example, by the method shown in Science of Petroleum, Vol. II. P.1281 (1938). It is more preferable if compound (Y11) contains a component having a boiling point of 280° C. or higher.

The percentage ratio of compound (Y11) to acrylic compound (Y) is preferably 50% by mass or more. In this case, the storage stability of composition (X) is effectively enhanced, outgassing from the cured product is effectively reduced, and the affinity of the cured product for water is particularly difficult to increase. The percentage ratio of the compound (Y11) to the acrylic compound (Y) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

The viscosity of compound (Y11) at 25° C. is preferably 25 mPa·s or less. In this case, compound (Y11) can lower the viscosity of composition (X). The viscosity of compound (Y11) at 25° C. is more preferably 25 mPa·s or less, still more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. The viscosity of compound (Y11) at 25° C. is, for example, 1 mPa·s or more, preferably 3 mPa·s or more, and more preferably 5 mPa·s or more.

Compound (Y11) is at least one compound selected from the group consisting of, for example, alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, and alkylene oxide-modified alkylene glycol di(meth)acrylates. contains.

Alkylene glycol di(meth)acrylate is a compound in which n is 1 in formula (200). In this case, R ³ in formula (200) preferably has 4 to 12 carbon atoms. R ³ may be linear or branched. In particular, alkylene glycol di(meth)acrylates are 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate. Acrylates, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol It preferably contains at least one compound selected from the group consisting of dimethacrylate, 1,10-decanediol dimethacrylate, and 1,12-dodecanediol dimethacrylate. In addition, alkylene glycol di (meth) acrylate, product number SR213 manufactured by Sartomer, product number V195 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number SR212 manufactured by Sartomer, product number SR247 manufactured by Sartomer, product name light acrylate manufactured by Kyoeisha Chemical Co., Ltd. NP-A, product number SR238NS manufactured by Sartomer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel, product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., product number V260 manufactured by Osaka Organic Chemical Industry Co., Ltd. , Product number 1,9-ND-A manufactured by Kyoei Chemical Industry Co., Ltd., Product number A-NOD-A manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product number CD595 manufactured by Sartomer, Product number SR214NS manufactured by Sartomer, Shin-Nakamura Chemical Industry Co., Ltd. BD, product number SR297 manufactured by Sartomer, product number SR248 manufactured by Sartomer, product name Light Ester NP manufactured by Kyoeisha Chemical, product number SR239NS manufactured by Sartomer, product name Light Ester 1,6HX manufactured by Kyoeisha Chemical, Shin-Nakamura Chemical Product number HD-N manufactured by Kogyosha, product name Light Ester 1,9ND manufactured by Kyoeisha Chemical Co., Ltd., product number NOD-N manufactured by Shin-Nakamura Chemical Co., Ltd., product name Light Ester 1,10DC manufactured by Kyoeisha Chemical Co., Ltd., Shin-Nakamura Chemical Industry Co., Ltd. It preferably contains at least one compound selected from the group consisting of product number DOD-N manufactured by Sartomer and product number SR262 manufactured by Sartomer.

Polyalkylene glycol di(meth)acrylate is, for example, a compound in which n is 2 or more in formula (200). n is, for example, 2 to 10, preferably 2 to 7, more preferably 2 to 6, and more preferably 2 to 3. The carbon number of R ³ is, for example, 2-7, preferably 2-5. The higher the number of carbon atoms, the higher the hydrophobicity of the cured product, and the more difficult it is for the cured product to permeate moisture. Polyalkylene glycol di(meth)acrylates are especially diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tripropylene glycol diacrylate, It preferably contains at least one compound selected from the group consisting of propylene glycol dimethacrylate, tritetramethylene glycol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. In addition, the polyalkylene glycol di(meth)acrylate is particularly available as product number SR230 manufactured by Sartomer, product number SR508NS manufactured by Sartomer, product number DPGDA manufactured by Daicel, product number SR306NS manufactured by Sartomer, product number TPGDA manufactured by Daicel, Osaka organic Product number V310HP manufactured by Kagaku Kogyo Co., Ltd., product number APG200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name Light Acrylate PTMGA-250 manufactured by Kyoeisha Chemical Co., Ltd., product number SR231NS manufactured by Sartomer, product name Light Ester 2EG manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Sartomer SR205NS, product name Light Ester 3EG manufactured by Kyoeisha Chemical Co., Ltd., product number SR210NS manufactured by Sartomer, product name Light Ester 4EG manufactured by Kyoeisha Chemical Co., Ltd., product name Acryester HX manufactured by Mitsubishi Chemical Corporation, and product number 3PG manufactured by Shin-Nakamura Chemical Co., Ltd. It is preferable to contain at least one compound selected from the group consisting of

Alkylene oxide-modified alkylene glycol di(meth)acrylates include, for example, propylene oxide-modified neopentyl glycol. In addition, the alkylene oxide-modified alkylene glycol di(meth)acrylate contains, for example, product number EBECRYL145 manufactured by Daicel.

When the acrylic compound (Y) contains the compound (Y11) having the structure represented by the formula (200), the compound (Y11) preferably does not contain compounds in which the value of n in the formula (200) is 5 or more. . It is particularly preferred not to include compounds in which the value of n in formula (200) is greater than 5 when (R ³ —O)n is a polyethylene glycol skeleton. Even when the compound (Y11) contains a compound in the formula (200) in which the value of n is greater than 5, the percentage of the compound in the formula (200) in which the value of n is greater than 5 relative to the acrylic compound (Y) is 20. % or less is preferable. Further, even when the compound (Y11) contains a compound having a value of n greater than 5 in the formula (200), the compound (Y11) preferably does not contain a compound having a value of n greater than 9. It is further preferred not to include compounds with a value greater than 7. In these cases, the increase in viscosity of composition (X) is particularly difficult to occur.

It is particularly preferred if the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di(meth)acrylate. Polyalkylene glycol di (meth) acrylate has a low viscosity and is difficult to volatilize, so it can contribute to lowering the viscosity of the composition (X), and improves the storage stability of the composition (X) and prevents the cured product from It can contribute to the reduction of outgassing.

When the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di(meth)acrylate, the ratio of polyalkylene glycol di(meth)acrylate to the acrylic compound (Y) is 40% by mass or more and 80% by mass or less. is preferred. When the proportion of polyalkylene glycol di(meth)acrylate is 40% by mass or more, the viscosity of composition (X) can be effectively reduced. This ratio is more preferably 42% by mass or more and 75% by mass or less, and even more preferably 45% by mass or more and 70% by mass or less.

The polyfunctional acrylic compound (Y1) may contain a compound having three or more radically polymerizable functional groups containing (meth)acryloyl groups in one molecule. In this case, the polyfunctional acrylic compound (Y1) can contain, for example, at least one selected from the group consisting of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and pentaerythritol tetra(meth)acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and therefore the heat resistance of the cured product can be particularly increased.

The polyfunctional acrylic compound (Y1) preferably contains pentaerythritol tetra(meth)acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and the reactivity of the composition (X) can be improved. When the reactivity of the composition (X) is improved, the composition (X) can be easily cured even in an oxygen-containing environment such as an air atmosphere.

When the polyfunctional acrylic compound (Y1) contains pentaerythritol tetra (meth) acrylate, the ratio of pentaerythritol tetra (meth) acrylate to the acrylic compound (Y) is 0.5% by mass or more and 10% by mass or less. is preferred. In this case, both high reactivity and low viscosity of composition (X) can be achieved. This ratio is more preferably 1% by mass or more and 9% by mass or less, and even more preferably 2% by mass or more and 8% by mass or less.

The polyfunctional acrylic compound (Y1) may have at least one of a benzene ring, an alicyclic ring and a polar group. A polar group is, for example, at least one of an OH group and an NHCO group. In this case, shrinkage during curing of the composition (X) can be particularly reduced. Furthermore, adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide can be enhanced. The polyfunctional acrylic compound (Y1) is at least selected from the group consisting of tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. It preferably contains one compound. These compounds can particularly reduce shrinkage when the composition (X) is cured. Furthermore, these compounds can also enhance the adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide.

If the adhesion between the cured product and the inorganic material is increased, the adhesion between the optical component and the inorganic film is high when the optical component is superimposed on a film made of an inorganic material (inorganic film) such as a SiN film. easy to get

It is particularly preferable if the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di(meth)acrylate and pentaerythritol tetra(meth)acrylate. In this case, the composition (X) has a low viscosity and excellent reactivity. Therefore, the composition (X) can be easily cured even in an environment containing oxygen such as an air atmosphere.

The acrylic compound (Y) also preferably contains a monofunctional acrylic compound (Y2) having only one (meth)acryloyl group as the radically polymerizable functional group in one molecule. The monofunctional acrylic compound (Y2) can suppress shrinkage during curing of the composition (X).

When the acrylic compound (Y) contains the monofunctional acrylic compound (Y2), the amount of the monofunctional acrylic compound (Y2) relative to the total amount of the acrylic compound (Y) is preferably more than 0% by mass and 50% by mass or less. . When the amount of the monofunctional acrylic compound (Y2) is more than 0% by mass, the shrinkage of the composition (X) during curing can be suppressed. In addition, when the amount of the monofunctional acrylic compound (Y2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (Y1) can be 50% by mass or more, so that the heat resistance of the cured product can be particularly improved. The amount of the monofunctional acrylic compound (Y2) is more preferably 5% by mass or more, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

Monofunctional acrylic compounds (Y2) include, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, and 2-methoxyethyl acrylate. , methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, imido acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol (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, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloylmorpholine, morpholin 4-yl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, It contains at least one compound selected from the group consisting of 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The monofunctional acrylic compound (Y2) may contain at least one compound selected from the group consisting of compounds having an alicyclic structure and compounds having a cyclic ether structure.

Compounds having an alicyclic structure include, for example, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, acryloylmorpholine , morpholin 4-yl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate. It contains at least one selected compound.

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

The acrylic compound (Y) may contain a compound having silicon in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having silicon in the molecular skeleton include, for example, 3-(trimethoxysilyl)propyl acrylate (eg product number KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth)acrylic group-containing alkoxysilane oligomer (eg manufactured by Shin-Etsu Chemical Co., Ltd. KR-513) containing at least one compound selected from the group consisting of product number KR-513).

The acrylic compound (Y) may contain a compound having phosphorus in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having phosphorus in the molecular backbone include acid phosphooxy (meth)acrylates, such as acid phosphooxy polyoxypropylene glycol monomethacrylate.

The acrylic compound (Y) may contain a compound having nitrogen in its molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. In addition, the reactivity of the acrylic compound (Y) is likely to be improved, so outgassing is less likely to occur from the cured product. In particular, acrylic compound (Y) preferably contains a compound having a —R—N— skeleton as the compound included in compound (A02) described above. The compound having nitrogen in the molecular skeleton is at least selected from the group consisting of compounds having a morpholine skeleton such as acryloylmorpholine and morpholin-4-yl acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. Contains a compound.

It is particularly preferred that the acrylic compound (Y) contains a compound having a morpholine skeleton. In this case, the reactivity of the composition (X) can be further improved, and the curability of the composition (X) can be further improved even in an air atmosphere. Further, since the morpholine skeleton includes the -R-O- skeleton and the -RN- skeleton, the compound having a morpholine skeleton is included in the compound (A02) described above. It is particularly preferred if the acrylic compound (Y) contains at least one of acryloylmorpholine and morpholin-4-yl acrylate. In this case, shrinkage of the composition (X) during curing can be suppressed. Also, acryloylmorpholine and morpholin-4-yl acrylate have low viscosities, so these compounds are less likely to increase the viscosity of composition (X). Furthermore, since these compounds are difficult to volatilize, it is easy to improve the storage stability of the composition (X).

The ratio of the compound having a morpholine skeleton to the acrylic compound (Y) is preferably 5% by mass or more and 50% by mass or less. In this case, there is an advantage that outgassing is less likely to occur from the cured product of the composition (X). This ratio is more preferably 7% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less.

Acrylic compound (Y) may contain a compound having an isobornyl skeleton. The compound having an isobornyl skeleton can contain, for example, one or more compounds selected from the group consisting of isobornyl acrylate and isobornyl methacrylate.

The acrylic compound (Y) may contain a component consisting of a compound having at least one skeleton selected from the group consisting of a dicyclopentadiene skeleton, a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. Specifically, the acrylic compound (Y) may contain at least one compound selected from the group consisting of, for example, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxy diacrylate and bisphenol F polyethoxy diacrylate. good. In this case, the adhesion between the cured product and the inorganic material can be enhanced.

The acrylic compound (Y) may contain a compound represented by the following formula (100). In this case, the reactivity of the composition (X) can be increased, and the adhesion between the cured product and the inorganic material can be improved.

In formula (100), R ⁰ is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of R ¹ to R ¹¹ is H, an alkyl group or -R ¹² -OH, R ¹² is an alkylene group and at least one of R ¹ to R ¹¹ is an alkyl group or -R ¹² -OH. R ¹ to R ¹¹ are not chemically bonded to each other. When X is a divalent hydrocarbon group, this compound has an —R—O— skeleton and is thus included in the above compound (A02).

Specifically, for example, the acrylic compound (Y) contains at least one compound selected from the group consisting of a compound represented by the following formula (110), a compound represented by the formula (120), and a compound represented by the formula (130). You may

The radically polymerizable compound (A1) may contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radically polymerizable compound (Z) with respect to the total amount of the acrylic compound (Y) and the radically polymerizable compound (Z) is, for example, 10% by mass or less. The radically polymerizable compound (Z) includes a polyfunctional radically polymerizable compound (Z1) having two or more radically polymerizable functional groups per molecule and a monofunctional compound having only one radically polymerizable functional group per molecule. At least one of the radically polymerizable compound (Z2) can be contained. The monofunctional radically polymerizable compound (Z2) is included in the monofunctional photopolymerizable compound (A011) described above, and the multifunctional radically polymerizable compound (Z1) is included in the polyfunctional photopolymerizable compound (A012) described above. be

The polyfunctional radically polymerizable compound (Z1) is, for example, a group consisting of aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers and other special oligomers having two or more ethylenic double bonds in one molecule. It may contain at least one compound selected from In addition, the components that the polyfunctional radically polymerizable compound (Z1) may contain are not limited to those described above. Monofunctional radically polymerizable compounds (Z2) include, for example, N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxidedecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam. In addition, the components that the monofunctional radically polymerizable compound (Z2) may contain are not limited to those described above.

When the radically polymerizable compound (A1) contains the radically polymerizable compound (Z), the radically polymerizable compound (Z) may contain a compound having nitrogen in its molecular skeleton. Compounds having nitrogen in the molecular skeleton include, for example, at least one compound selected from the group consisting of N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. In this case, as in the case where the acrylic compound (Y) contains a compound having nitrogen in its molecular skeleton, the adhesion between the cured product and the inorganic material is improved.

In other words, the radically polymerizable compound (A1) preferably contains a compound having nitrogen in its molecular skeleton. The compound having nitrogen in its molecular skeleton may contain a compound contained in the acrylic compound (Y), or may contain a compound contained in the radically polymerizable compound (Z). In this case, the adhesion between the cured product and the inorganic material is improved. The ratio of the compound having nitrogen in the molecular skeleton to the entire radically polymerizable compound (A1) is preferably 5% by mass or more and 80% by mass or less. When this ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton is less likely to inhibit the storage stability of the composition (X), and the satellite when the composition (X) is jetted by an inkjet method. difficult to generate. Therefore, the inkjet properties of the composition (X) are less likely to be impaired. Furthermore, outgassing due to compounds having nitrogen in the molecular skeleton can be suppressed. This ratio is more preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less.

The total number of monofunctional radically polymerizable compounds in the radically polymerizable compound (A1) (that is, the total of the monofunctional acrylic compound (Y2) and the monofunctional radically polymerizable compound (Z2)) relative to the radically polymerizable compound (A1). The proportion is preferably 70% by mass or less. In this case, outgassing due to the monofunctional compound is less likely to occur. This ratio is more preferably 60% by mass or less, and even more preferably 50% by mass or less.

The radical photopolymerization initiator (B1) is not particularly limited as long as it is a compound that generates radical species when irradiated with light. The radical photopolymerization initiator (B1) preferably contains a compound that generates radical species when irradiated with light having a peak wavelength of 395 nm.

Photoradical polymerization initiators (B1) include, for example, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds. , 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.

The ratio of the radical photopolymerization initiator (B1) to the radically polymerizable compound (A1) 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 air atmosphere. This ratio is more preferably 7% by mass or more, and even more preferably 8% by mass or more. The ratio is, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 18% by mass or less.

The radical photopolymerization initiator (B1) preferably contains a radical photopolymerization initiator (B1) having photobleaching properties. In this case, the cured product of composition (X) tends to have good light transmittance. The ratio of the radical photopolymerization initiator (B1) to the radically polymerizable compound (A1) 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. The ratio is, for example, 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less.

The radical photopolymerization initiator (B1) contains, for example, at least one of an acylphosphine oxide photoinitiator and a photobleaching compound among oxime ester photoinitiators.

The radical photopolymerization initiator (B1) also preferably contains 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. That is, the radical photopolymerization initiator (B1) preferably contains a component having at least one of a 9H-thioxanthene-9-one skeleton and an anthracene skeleton.

The radical photopolymerization initiator (B1) also preferably contains an oxime ester photoinitiator regardless of the presence or absence of photobleaching properties. The oxime ester photoinitiator can improve the curability of the composition (X). Therefore, the composition (X) can be easily cured even in an oxygen-containing environment such as an air atmosphere, and outgassing from the cured product can be suppressed.

The oxime ester-based photoinitiator has a fragrance in order to make the composition (X) and production equipment less likely to be contaminated by decomposition products from the composition (X), and to further make outgassing from the cured product less likely to occur. It preferably contains a compound having a ring, more preferably contains a compound having a condensed ring containing an aromatic ring, and further preferably contains a compound having a condensed ring containing a benzene ring and a hetero ring.

Oxime ester photoinitiators include, for example, 1,2-octadione-1-[4-(phenylthio)-, 2-(o-benzoyloxime)] and ethanone, 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), and JP 2000-80068, JP 2001-233842, JP 2010-527339, JP 2010- 527338, JP-A-2013-041153, JP-A-2015-93842, etc. can contain at least one compound selected from the group consisting of oxime ester photoinitiators. The oxime ester-based photoinitiators are commercially available products having a carbazole skeleton, Irgacure OXE-02 (manufactured by BASF), Adeka Arcules NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (Changzhou Kyokuden Denshi). New Material Co., Ltd.), Irgacure OXE-01 having a diphenyl sulfide skeleton, ADEKA Arkles NCI-930 (ADEKA Co., Ltd.), TR-PBG-345 and TR-PBG-3057 (all of these, Changzhou Tenryu Denshi New Materials Co., Ltd.) , and at least one compound selected from the group consisting of TR-PBG-365 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.) and SPI-04 (manufactured by Sanyang) having a fluorene skeleton. In particular, when the oxime ester photoinitiator contains a compound having a diphenyl sulfide skeleton or a fluorene skeleton, it is preferable in that the cured product is less likely to be colored by photobleaching. It is also preferable that the oxime ester-based photoinitiator contains a compound having a carbazole skeleton, since exposure sensitivity tends to increase.

It is also preferred that the oxime ester photoinitiator contains two or more compounds. In this case, for example, the oxime ester photoinitiator contains two or more compounds with different exposure sensitivities, so that the amount of the radical photopolymerization initiator (B1) can be reduced while maintaining good exposure sensitivity. Therefore, outgassing from the cured product can be further suppressed.

The oxime ester compound having photobleaching properties contains, for example, at least one of a compound represented by the following formula (401) and a compound represented by the following formula (402). Among these, the compound represented by the formula (402) has particularly high sensitivity, so that the photocurability of the composition (X) is particularly likely to be enhanced, and therefore the photocurability of the composition (X) in an air atmosphere is easily realized. .

When the radical photopolymerization initiator (B1) contains an acylphosphine oxide compound, even if it contains an ultraviolet absorber (C), the reactivity of the composition (X) when irradiated with light tends to be higher. In particular, the reactivity of the composition (X) tends to increase when irradiated with light having a wavelength of 395 nm. The percentage of the acylphosphine oxide compound relative to the total photoradical polymerization initiator (B1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. The acylphosphine oxide compound contains, for example, at least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

The composition (X) may contain a polymerization accelerator in addition to the radical photopolymerization initiator (B1). Polymerization accelerators include, for example, ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl. In addition, the components that the polymerization accelerator may contain are not limited to those mentioned above.

The cationic polymerizable compound (A2) will be explained. When the photopolymerizable compound (A) contains the cationically polymerizable compound (A2), the cationically polymerizable compound (A2) is, for example, a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). contains at least one of

The polyfunctional cationically polymerizable compound (W1) is one or both of a polyfunctional cationically polymerizable compound (W11) having no siloxane skeleton and a polyfunctional cationically polymerizable compound (W12) having a siloxane skeleton. can contain

The polyfunctional cationically polymerizable compound (W11) does not have a siloxane skeleton and has two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (W11) is preferably 2 to 4, more preferably 2 to 3.

The cationic polymerizable functional group is, for example, at least one group selected from the group consisting of cyclic ether groups and vinyl ether groups. The cyclic ether group is, for example, at least one of an epoxy group and an oxetane group.

The polyfunctional cationically polymerizable compound (W11) is, for example, from the group consisting of polyfunctional alicyclic epoxy compounds, polyfunctional heterocyclic epoxy compounds, polyfunctional oxetane compounds, alkylene glycol diglycidyl ethers, and alkylene glycol monovinyl monoglycidyl ethers. It contains at least one selected compound.

The polyfunctional alicyclic epoxy compound contains, for example, one or both of a compound represented by the following formula (1) and a compound represented by the following formula (20).

In formula (1), each of R ¹ to R ¹⁸ is independently a hydrogen atom, a halogen atom, or a hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably within the range of 1-20. The hydrocarbon group is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an ethylidene group or a propylidene group. 20 alkylidene groups. The hydrocarbon group may contain an oxygen atom or a halogen atom. Each of R ¹ to R ¹⁸ is independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

In Formula (1), X is a single bond or a divalent organic group. The organic group is, for example, --CO--O--CH ₂ --, and in this case the compound represented by formula (1) is included in the compound (A02) described above.

Examples of the compound represented by formula (1) include the compound represented by formula (1a) below and the compound represented by formula (1b) below.

In formula (20), each of R ¹ to R ¹² is independently a hydrogen atom, a halogen atom, or a
20 hydrocarbon groups. Halogen is, for example, fluorine, chlorine, bromine or iodine. The hydrocarbon group having 1 to 20 carbon atoms is, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; or an ethylidene group and a propylidene group. It is an alkylidene group having 2 to 20 carbon atoms such as a group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

Each of R ¹ to R ¹² is independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

Examples of compounds represented by formula (20) include tetrahydroindene diepoxide represented by formula (20a) below.

A polyfunctional heterocyclic epoxy compound contains, for example, a trifunctional epoxy compound as represented by the following formula (2).

The polyfunctional oxetane compound contains, for example, a bifunctional oxetane compound represented by the following formula (3).

Alkylene glycol diglycidyl ether contains, for example, at least one compound selected from the group consisting of compounds represented by the following formulas (4) to (7).

Alkylene glycol monovinyl monoglycidyl ether contains, for example, a compound represented by the following formula (8).

Compounds represented by formulas (2) to (8) above are included in the compound (A02) above.

More specifically, the polyfunctional cationically polymerizable compound (W11) is, for example, Celoxide 2021P and Celoxide 8010 manufactured by Daicel, TEPIC-VL manufactured by Nissan Chemical, OXT-221 manufactured by Toagosei, and 1, manufactured by Yokkaichi Gosei. It can contain at least one component selected from the group consisting of 3-PD-DEP, 1,4-BG-DEP, 1,6-HD-DEP, NPG-DEP and butylene glycol monovinyl monoglycidyl ether.

The polyfunctional cationically polymerizable compound (W11) also preferably contains a polyfunctional alicyclic epoxy compound. In this case, the composition (X) can have a particularly high cationic polymerization reactivity.

The polyfunctional alicyclic epoxy compound preferably contains either one or both of the compound represented by formula (1) and the compound represented by formula (20). In this case, composition (X) can have higher cationic polymerization reactivity.

When the polyfunctional alicyclic epoxy compound contains the compound represented by formula (1), the compound represented by formula (1) preferably contains the compound represented by formula (1a). In this case, the composition (X) can have a higher cationic polymerization reactivity and a particularly low viscosity.

In addition, in particular, the compound represented by formula (20) has a low viscosity, so when the compound represented by formula (20) is contained, the composition (X) can have good photocurability, and in particular It can have a low viscosity. Furthermore, the compound represented by formula (20) has a property of being difficult to volatilize in spite of having a low viscosity. Therefore, even if the composition (X) contains the compound represented by the formula (20), the composition (X) is unlikely to change in composition due to volatilization of the compound represented by the formula (20). Therefore, by containing the compound represented by formula (20), the composition (X) can have a low viscosity without impairing the storage stability.

The compound represented by formula (20) can be synthesized, for example, by oxidizing a cyclic olefin compound having a tetrahydroindene skeleton using an oxidizing agent.

The compound of formula (20) can contain four stereoisomers based on the configuration of the two epoxy rings. Compounds of formula (20) may include any of the four stereoisomers. That is, the compound represented by formula (20) can contain at least one component selected from the group consisting of four stereoisomers. In the compound represented by formula (20), the total percentage of the exo-endo isomer and endo-endo isomer among the four stereoisomers should be 10% by mass or less with respect to the entire epoxy compound (A1). is preferred, and 5% by mass or less is more preferred. In this case, the heat resistance of the cured product can be improved. The percentage of a specific stereoisomer in the compound represented by formula (20) can be determined based on the peak area ratio appearing in the chromatogram obtained by gas chromatography.

In order to reduce the amounts of the exo-endo form and the endo-endo form in the compound represented by the formula (20), a method of precision distillation of the compound represented by the formula (20), column chromatography using silica gel or the like as a packing material Any suitable method can be applied, such as a method applying graphics.

When the composition (X) contains the polyfunctional cationically polymerizable compound (W11), the percentage of the polyfunctional cationically polymerizable compound (W11) to the total amount of the resin component is preferably 5% by mass or more and 95% by mass or less. . The resin component refers to a cationically polymerizable compound in the composition (X), and includes a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). If the percentage of the polyfunctional cationically polymerizable compound (W11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity during the cationic photopolymerization reaction, and thereby the cured product has high strength. (hardness). Further, if the percentage of the polyfunctional cationically polymerizable compound (W11) is 95% by mass or less, when the composition (X) contains the moisture absorbent (E), the moisture absorbent (E ) can be particularly easily dispersed uniformly. The percentage of the polyfunctional cationically polymerizable compound (W11) is more preferably 12% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. is particularly preferred. The percentage of the polyfunctional cationically polymerizable compound (W11) is more preferably 85% by mass or less, and even more preferably 60% by mass or less. For example, it is preferable that the percentage of the polyfunctional cationically polymerizable compound (W11) is within the range of 20 to 60% by mass.

When the polyfunctional cationically polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be part or all of the polyfunctional cationically polymerizable compound (W11). may be The percentage ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (W11) is preferably 15% by mass or more and 100% by mass or less. When this percentage is 15% by mass or more, the polyfunctional alicyclic epoxy compound can particularly contribute to improving the photocurability of the composition (X).

The polyfunctional cationically polymerizable compound (W12) has a siloxane skeleton and two or more cationically polymerizable functional groups per molecule. The number of cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (W12) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cationically polymerizable compound (W12) can contribute to improving the cationic polymerization reactivity of the composition (X), and can contribute to improving the resistance to heat discoloration of the cured product and the optical component. The polyfunctional cationically polymerizable compound (W12) can also contribute to lower elastic modulus of cured products and optical parts. When the composition (X) contains a moisture absorbent, the polyfunctional cationically polymerizable compound (W12) can also contribute to improving the dispersibility of the moisture absorbent in the composition (X) and in the cured product.

The polyfunctional cationic polymerizable compound (W12) is preferably liquid at 25°C. In particular, the viscosity at 25° C. of the polyfunctional cationic polymerizable compound (W12) is preferably in the range of 10 to 300 mPa·s. In this case, an increase in the viscosity of composition (X) can be suppressed.

The cationically polymerizable functional group possessed by the polyfunctional cationically polymerizable compound (W12) is, for example, at least one group selected from the group consisting of an epoxy group, an oxetane group and a vinyl ether group.

The siloxane skeleton of the polyfunctional cationically polymerizable compound (W12) may be linear, branched, or cyclic. The number of Si atoms in the siloxane skeleton is preferably within the range of 2-14. In this case, composition (X) can have a particularly low viscosity. The number of Si atoms is more preferably within the range of 2-10, more preferably within the range of 2-7, and particularly preferably within the range of 3-6.

The polyfunctional cationically polymerizable compound (W12) contains, for example, at least one of the compound represented by formula (10) and the compound represented by formula (11).

R in each of formulas (10) and (11) is a single bond or a divalent organic group, preferably an alkylene group. Y is a siloxane skeleton, which may be linear, branched, or cyclic, and the number of Si atoms is preferably within the range of 2 to 14, preferably within the range of 2 to 10. is more preferable, more preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6. n is an integer of 2 or more, preferably in the range of 2-4.

More specifically, for example, the polyfunctional cationic polymerizable compound (W12) contains a compound represented by the following formula (10a).

R in formula (10a) is a single bond or a divalent organic group, preferably an alkylene group having 1 to 4 carbon atoms. n in formula (10a) is an integer of 0 or more. n is preferably in the range of 0 to 12, more preferably in the range of 0 to 8, still more preferably in the range of 0 to 5, and particularly in the range of 1 to 4 preferable.

The compound represented by formula (10a) preferably contains a compound represented by formula (30) described later. That is, the polyfunctional cationic polymerizable compound (W12) preferably contains a compound represented by the following formula (30).

More specifically, the polyfunctional cationic polymerizable compound (W12) is, for example, Shin-Etsu Chemical Co., Ltd. product numbers X-40-2669, X-40-2670, X-40-2715, X-40-2732, X -Containing at least one component selected from the group consisting of 22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B is preferred.

The polyfunctional cationically polymerizable compound (W12) preferably has an alicyclic epoxy structure, and it is particularly preferable if the polyfunctional cationically polymerizable compound (W12) contains a compound represented by formula (10a). The compound represented by the formula (10a) can particularly contribute to improving the cationic polymerization reactivity and lowering the viscosity of the composition (X). can contribute. When the composition (X) contains the moisture absorbent (E), it can particularly contribute to improving the dispersibility of the moisture absorbent (E) in the composition (X).

When the composition (X) contains the polyfunctional cationically polymerizable compound (W12), the percentage of the polyfunctional cationically polymerizable compound (W12) to the total amount of the resin component is preferably 5% by mass or more and 95% by mass or less. . In this case, especially when the composition (X) contains the moisture absorbent (E), the dispersibility of the moisture absorbent (E) in the composition (X) and in the cured product is particularly improved, and the composition (X) can have a particularly high photocationic polymerization reactivity.

The monofunctional cationically polymerizable compound (W2) has only one cationically polymerizable functional group per molecule. The cationic polymerizable functional group is, for example, at least one group selected from the group consisting of epoxy group, oxetane group and vinyl ether group.

The viscosity of the monofunctional cationically polymerizable compound (W2) at 25° C. is preferably 8 mPa·s or less. In this case, the monofunctional cationic polymerizable compound (W2) can reduce the viscosity of the composition (X) even if the composition (X) does not contain a solvent. In particular, the viscosity of the monofunctional cationic polymerizable compound (W2) at 25° C. is preferably in the range of 0.1 to 8 mPa·s.

The monofunctional cationically polymerizable compound (W2) can contain, for example, at least one compound selected from the group consisting of compounds represented by the following formulas (12) to (17) and limonene oxide.

Compounds represented by formulas (12) to (14), (16) and (17) above are included in compound (A02) above.

The percentage of the monofunctional cationically polymerizable compound (W2) with respect to the total amount of the resin component is preferably 5% by mass or more and 50% by mass or less. If the percentage of the monofunctional cationic polymerizable compound (W2) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. Further, when the percentage of the monofunctional cationically polymerizable compound (W2) is 50% by mass or less, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, and thereby, the cured product can have high strength (hardness). The percentage of the monofunctional cationically polymerizable compound (W2) is more preferably 10% by mass or more, and even more preferably 15% by mass or more. The percentage of the monofunctional cationically polymerizable compound (W2) is more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. Especially when the percentage of the monofunctional cationically polymerizable compound (W2) is 35% by mass or less, the amount of volatilization of the components in the composition (X) during storage of the composition (X) can be effectively reduced. Therefore, even if the composition (X) is stored for a long period of time, the properties of the composition (X) are unlikely to be impaired. Furthermore, it is possible to particularly suppress the generation of tack in the cured product. For example, it is preferable that the percentage of the monofunctional cationic polymerizable compound (W2) is within the range of 10 to 35% by mass.

Further, particularly when the composition (X) contains the polyfunctional cationically polymerizable compound (W11) and the polyfunctional cationically polymerizable compound (W12), the total amount of the resin component is is 30% by mass or more and 60% by mass or less, the percentage of the polyfunctional cationically polymerizable compound (W12) is 15% by mass or more and 30% by mass or less, and the percentage of the monofunctional cationically polymerizable compound (W2) is 15% by mass or more. It is preferably 40% by mass or less. In this case, good storage stability, low viscosity, and good cationic polymerization reactivity of the composition (X) can be achieved in a well-balanced manner. and a high refractive index can be achieved in good balance.

If the cationic polymerizable compound (A2) contains the compound represented by the formula (3) and the compound represented by the formula (16), a photocured product can be produced from the composition (X) by adjusting the ratio of the two. It is possible to realize a low viscosity and an improvement in the storage stability of the composition (X) while appropriately adjusting the easiness of progress of the curing reaction when the composition (X) is used.

The amount of the compound represented by formula (16) is appropriately adjusted so that the composition (X) has the properties described above. For example, the amount of the compound represented by formula (16) is preferably 10% by mass or more and 40% by mass or less with respect to the total amount of the resin component.

The cationically polymerizable compound (A2) preferably contains a compound (f1) represented by the following formula (30) (hereinafter also referred to as an aromatic epoxy compound (f1)).

In formula (30), X is at least one selected from the group consisting of halogen, H, a hydrocarbon group and an alkylene glycol group, and when there are multiple Xs in one molecule, they may be the same or different. may Hydrocarbon groups are, for example, alkyl groups or aryl groups. When X is a hydrocarbon group, the number of carbon atoms in X is in the range of 1 to 10, for example. R is a single bond or a divalent organic group. When R is a divalent organic group, the divalent organic group is, for example, an alkylene group, an oxyalkylene group, a carbonyloxyalkylene group (eg -CO-O-CH ₂ -), or -C(Ph) ₂ -O —CH ₂ — group. Y is H or a monovalent organic group. In addition, when R is an oxyalkylene group or a carbonyloxyalkylene group, the compound represented by the formula (30) is included in the compound (A02) described above. When Y is a monovalent organic group, the monovalent organic group is for example an alkyl group or an aryl group.

When the cationically polymerizable compound (A2) contains the aromatic epoxy compound (f1), the aromatic epoxy compound (f1) has a low viscosity, so the aromatic epoxy compound (f1) reduces the viscosity of the composition (X). easy to let In addition, the aromatic epoxy compound (f1) is difficult to volatilize, so even if the composition (X) is stored, the composition (X) is unlikely to change in composition due to volatilization of the aromatic epoxy compound (f1). . Therefore, the aromatic epoxy compound (f1) tends to improve the storage stability of the composition (X). In addition, since the aromatic epoxy compound (f1) has high reactivity, it is difficult for unreacted components to remain in the cured product, and thus outgassing is less likely to occur from the cured product. Furthermore, the aromatic epoxy compound (f1) tends to increase the glass transition temperature of the cured product, and therefore tends to increase the heat resistance of the cured product.

In addition, the aromatic epoxy compound (f1) is less likely to produce defective droplets called satellites when the composition (X) is ejected by an inkjet method.

R in formula (30) is preferably a single bond or an alkylene group. When n in formula (30) is 2 or 3, at least one of the multiple Rs in formula (30) is preferably a single bond or an alkylene group. In these cases, the reactivity of the aromatic epoxy compound (f1) tends to be high, so that the curability of the composition (X) tends to be high when the composition (X) is irradiated with ultraviolet rays.

The aromatic epoxy compound (f1) preferably contains, for example, at least one compound selected from the group consisting of compounds represented by formulas (301) to (318) below.

Compounds represented by formulas (306) to (311), (313), and (315) to (318) above are included in compound (A02) above.

In particular, the aromatic epoxy compound (f1) may contain at least one component selected from the group consisting of compounds represented by formulas (301) to (305), (312), (314) and (318). preferable. These compounds tend to have high reactivity because at least one epoxy group (oxirane) in the compound and a benzene ring are bonded via a single bond or an alkylene group, so that the composition (X) can be cured. easy to enhance.

The percentage ratio of the aromatic epoxy compound (f1) to the total cationically polymerizable compound (A2) is preferably 5% by mass or more. In this case, the above effects of the aromatic epoxy compound (f1) are particularly likely to be obtained. It is also preferred that this percentage is 95% by weight or less. In this case, the storage stability of the composition (X) tends to be good. This percentage is more preferably 10% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 85% by mass or less.

The cationically polymerizable compound (A2) may contain a compound (f2) having an oxyalkylene skeleton. An oxyalkylene skeleton is a linear skeleton composed of one or more linear oxyalkylene units. In addition, the compound (f2) having an oxyalkylene skeleton is included in the compound (A02) described above.

When the cationically polymerizable compound (A2) contains the compound (f2), the compound (f2) has a low viscosity, so the compound (f2) tends to reduce the viscosity of the composition (X). In addition, the compound (f2) is difficult to volatilize, so even when the composition (X) is stored, the composition (X) is less likely to change in composition due to volatilization of the aromatic epoxy compound (f1). Therefore, compound (f2) tends to improve the storage stability of composition (X).

In addition, the compound (f2) is less likely to produce defective droplets called satellites when the composition (X) is ejected by an inkjet method. Furthermore, the compound (f2) can suppress the formation of satellites even when the speed of droplets ejected by the inkjet method is increased. Therefore, depending on the inkjet conditions, for example, it is possible to increase the ejection speed of droplets by the inkjet method to 4 m/s or more without generating satellites. If the velocity of the droplets can be increased, the trajectory of the droplets is less likely to be affected by disturbance, so that the dimensional accuracy of the cured product produced from the composition (X) can be enhanced. Furthermore, since the compound (f2) can enhance the storage stability of the composition (X) as described above, the composition (X) is unlikely to form satellites even when the composition (X) is stored for a long period of time. characteristics are easily maintained.

The oxyalkylene skeleton particularly preferably has the structure “—C—C—O—”, that is, contains oxyethylene units. In this case, satellites are particularly unlikely to occur, and for example, satellites are less likely to occur even if the driving frequency for ejecting the composition (X) is changed by an ink jet method. In addition, the compound (f2) is less likely to volatilize and tends to have a lower viscosity, and the affinity (wettability) of the composition (X) for inorganic materials tends to increase.

The number of oxyalkylene units in the oxyalkylene skeleton in compound (f2) is preferably 1 or more and 8 or less. In this case, since the compound (f2) tends to have a lower viscosity, satellites are particularly unlikely to form, and the crosslink density of the cured product tends to increase, so the glass transition temperature of the cured product tends to increase. The number of oxyalkylene units is more preferably 1 or more and 6 or less, and more preferably 1 or more and 4 or less.

A substituent other than hydrogen may be bonded to the oxyalkylene unit in the oxyalkylene skeleton of the compound (f2). For example, an oxyethylene unit contained in an oxyalkylene skeleton may have a structure of "--CH _{( CH.sub.3} )--CH.sub.2--O--".

The percentage of the compound (f2) is preferably 10% by mass or more relative to the cationic polymerizable compound (A2). In this case, the ink-jet property is improved and the wettability to the substrate is improved. It is also preferred that this percentage is 70% by weight or less. In this case, the glass transition temperature can be sufficiently increased. This percentage is more preferably 15% by mass or more and 60% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less.

The compound (f2) contains, for example, at least one compound selected from a compound (f21) having an oxyalkylene skeleton and an epoxy group and a compound (f22) having an oxyalkylene group and an oxetane group.

The compound (f21) is, for example, the compound represented by the above formula (1b), the compound represented by the formula (4), the compound represented by the formula (5), the compound represented by the formula (6), the compound represented by the formula (7), the compound represented by the formula It contains at least one compound selected from the group consisting of the compound represented by (8), the compound represented by formula (13), the compound represented by formula (14), and the like. In addition, the components that the compound (f21) may contain are not limited to those mentioned above.

The compound (f22) is at least one selected from the group consisting of, for example, the compound represented by the above formula (3), the compound represented by the formula (12), the compound represented by the formula (16), and the compound represented by the formula (17). contains a compound of In addition, the components that the compound (f22) may contain are not limited to those mentioned above.

When the composition (X) contains the cationically polymerizable compound (A2), the composition (X) preferably further contains a sensitizer. In this case, the composition (X) can have a particularly high cationic polymerization reactivity. The sensitizer contains, for example, one or both of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene. The percentage ratio of the sensitizer to the cationic polymerizable compound (A2) is preferably in the range of more than 0 mass % and 1 mass % or less. In this case, the sensitizer hardly inhibits the transparency (visible light transmittance) of the cured product, so that the cured product can have good transparency (visible light transmittance).

When the composition (X) contains the cationic polymerizable compound (A2), the photopolymerization initiator (B) preferably contains the photocationic polymerization initiator (B2). The photocationic polymerization initiator (B2) is not particularly limited as long as it is a catalyst that generates protonic acid or Lewis acid upon receiving light irradiation. The photocationic polymerization initiator (B2) preferably contains a catalyst that generates protonic acid or Lewis acid upon irradiation with light having a peak wavelength of 395 nm. The photocationic polymerization initiator (B2) can contain at least one of an ionic photoacid-generating cationic curing catalyst and a nonionic photoacid-generating cationic curing catalyst.

The ionic photoacid-generating cationic curing catalyst can contain at least one of onium salts and organometallic complexes. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of organometallic complexes include iron-arene complexes, titanocene complexes, and arylsilanol-aluminum complexes. The ionic photoacid-generating cationic curing catalyst can contain at least one of these components.

The nonionic photoacid-generating cationic curing catalyst is, for example, at least one selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide phosphonates. can contain the components of The components that the nonionic photoacid-generating cationic curing catalyst can contain are not limited to those described above.

More specific examples of compounds that can be contained in the photocationic polymerization initiator (B2) include Midori Chemical DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, 109, etc.), BBI series (101, 102, 103, 105, 106, 109, 110, 200, 210, 300, 301, etc.), TSP series (102, 103, 105, 106, 109, 200, 300, 1000, etc.) ), HDS-109, MDS series (103, 105, 109, 203, 205, 209, etc.), BDS-109, MNPS-109, DTS series (102, 103, 105, 200, etc.), NDS series (103, 105 , 155, 165, etc.), DAM series (101, 102, 103, 105, 201, etc.), SI series (105, 106, etc.), PI-106, NDI series (105, 106, 109, 1001, 1004, etc.), PAI series (01, 101, 106, 1001, 1002, 1003, 1004, etc.), MBZ-101, PYR-100, NB series (101, 201, etc.), NAI series (100, 1002, 1003, 1004, 101, 105 , 106, 109, etc.), TAZ series (100, 101, 102, 103, 104, 107, 108, 109, 110, 113, 114, 118, 122, 123, 203, 204, etc.), NBC-101, ANC- 101, TPS-Acetate, DTS-Acetate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butyl cholate, BX, BC-2, MPI-103, BDS-105, TPS-103, NAT -103, BMS-105, and TMS-105;
Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950 manufactured by Union Carbide, USA;
Irgacure 250, Irgacure 261 and Irgacure 264 from BASF;
CG-24-61 manufactured by Ciba-Geigy;
Adeka Optomer SP-150, Adeka Optomer SP-151, Adeka Optomer SP-170 and Adeka Optomer SP-171 manufactured by ADEKA Corporation;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd.;
CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682 manufactured by Nippon Soda Co., Ltd;
PI-2074, a tetrakis(pentafluorophenyl)borate toluyl cumyl iodonium salt from Rhodia;
FFC509 manufactured by 3M;
CD-1010, CD-1011 and CD-1012 manufactured by Sartomer, USA;
CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S from Sun-Apro Corporation; and UVI-6992 and UVI-6976 from The Dow Chemical Company. The photocationic polymerization initiator (B2) can contain at least one compound selected from the group consisting of these compounds.

The photocationic polymerization initiator (B2) preferably has a triarylsulfonate-type cation. In particular, the photocationic polymerization initiator (B2) is selected from the group consisting of a cation represented by the following formula (61), a cation represented by the formula (62), a cation represented by the formula (63), and a cation represented by the following formula (64). It is preferred to contain a salt having at least one kind of cation. In this case, the cationic photopolymerization initiator (B2) can effectively advance the reaction of the cationic polymerizable compound (A2) upon receiving light irradiation with a peak wavelength of 395 nm.

It is also preferred that the photocationic polymerization initiator (B2) contains a salt having a (perfluoroalkyl)fluorophosphate anion. In this case, the transparency (visible light transmittance) of the cured product tends to increase. The percentage of the salt having a (perfluoroalkyl)fluorophosphate anion with respect to the total photocationic polymerization initiator (B2) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, It is more preferable if it is 0.8% by mass or more.

A (perfluoroalkyl)fluorophosphate anion is represented by (Rf) _n PF _6-n ^— . Rf is a perfluoroalkyl group and n is any number from 1 to 5. The carbon number of Rf is, for example, 1 or more and 3 or less, and when there are a plurality of Rfs (when n is 2 or more), the Rfs may be the same or different.

It is also preferred that the salt having a (perfluoroalkyl)fluorophosphate anion has a triarylsulfonate-type cation, i.e. a salt of a triarylsulfonate-type cation and a (perfluoroalkyl)fluorophosphate anion. .

The percentage of the cationic photopolymerization initiator (B2) to the cationic polymerizable compound (A2) is preferably 1% by mass or more and 4% by mass or less. When this percentage is 1% by mass or more, the composition (X) can have particularly good cationic polymerization reactivity. In addition, since this percentage is 4% by mass or less, the composition (X) can have good storage stability, and the production cost can be reduced by not containing an excessive photocationic polymerization initiator (B2). is possible.

Next, the ultraviolet absorber (C) will be explained. As described above, the UV absorber (C) can reduce the UV transmittance of the cured product. In addition, the ultraviolet absorber (C) is less likely to inhibit the transmission of visible light than light reflecting materials such as titanium dioxide particles and zinc oxide particles.

UV absorbers (C) include benzotriazole UV absorbers, benzophenone UV absorbers, azomethine UV absorbers, indole UV absorbers, diazine UV absorbers, triazine UV absorbers, and pyrazolidinedione UV absorbers. It contains at least one selected from the group consisting of ultraviolet absorbers and ethylene-based ultraviolet absorbers. In this case, bleeding out of the ultraviolet absorber (C) is even less likely to occur, and the ultraviolet transmittance of the cured product is more likely to be reduced.

The ultraviolet absorbent (C) contains at least one of the reactive ultraviolet absorbent (C1) and the non-reactive ultraviolet absorbent (C2). The reactive ultraviolet absorber (C1) is an ultraviolet absorber capable of undergoing a polymerization reaction with at least one compound contained in the photopolymerizable compound (A). The non-reactive ultraviolet absorber (C2) is an ultraviolet absorber that does not undergo a polymerization reaction with the photopolymerizable compound (A).

When the ultraviolet absorbent (C) contains the reactive ultraviolet absorbent (C1), the ultraviolet absorbent (C) is less likely to bleed out from the cured product. It is speculated that this is because the reactive ultraviolet absorber (C1) reacts with the compound in the photopolymerizable compound (A) and is easily incorporated into the polymer skeleton in the cured product.

The reactive ultraviolet absorber (C1) preferably has a functional group (reactive functional group) having reactivity with the compound contained in the photopolymerizable compound (A). For example, when the photopolymerizable compound (A) contains a radically polymerizable compound, the reactive ultraviolet absorber (C1) preferably has a radically polymerizable functional group as a reactive functional group. Examples of radically polymerizable functional groups include ethylenically unsaturated groups. When the photopolymerizable compound (A) contains a cationic polymerizable compound, the reactive ultraviolet absorber (C1) preferably has a cationic polymerizable functional group as a reactive functional group. The cationic polymerizable functional group includes, for example, at least one selected from the group consisting of epoxy group, oxetane group and vinyl ether group.

The reactive ultraviolet absorber (C1) is, for example, a benzotriazole-based reactive ultraviolet absorber, a benzophenone-based reactive ultraviolet absorber, an azomethine-based reactive ultraviolet absorber, an indole-based reactive ultraviolet absorber, or a diazine-based reactive ultraviolet absorber. agent, a triazine-based reactive UV absorber, a pyrazolidinedione-based reactive UV absorber, and an ethylene-based reactive UV absorber.

In particular, the reactive ultraviolet absorber (C1) preferably contains at least one of a benzotriazole-based reactive ultraviolet absorber and a benzophenone-based reactive ultraviolet absorber. In this case, the benzotriazole-based reactive ultraviolet absorber and the benzophenone-based reactive ultraviolet absorber tend to absorb relatively short wavelength ultraviolet light. Therefore, the cured product becomes more difficult to transmit ultraviolet rays, and the transmission of visible light is less likely to be inhibited by the reactive ultraviolet absorber (C1). It is particularly preferred that the reactive ultraviolet absorber (C1) contains a benzotriazole-based reactive ultraviolet absorber. Since the benzotriazole-based reactive ultraviolet absorber can absorb ultraviolet rays in a relatively wide wavelength range, the cured product becomes particularly difficult to transmit ultraviolet rays.

A benzotriazole-based reactive ultraviolet absorber has, for example, a structure represented by the following formula (80).

In the above formula (80), the multiple Rs include at least one organic group having a reactive functional group. For example, among a plurality of R, one R or each of two R is preferably an organic group having a reactive functional group.

When the photopolymerizable compound (A) contains a radically polymerizable compound and the reactive functional group is a radically polymerizable functional group, the organic group having a reactive functional group is, for example, an organic group, an organic group represented by formula (82) or an organic group represented by formula (83). In formula (81) above, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. In the above formula (82), R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, X ¹ is O, S, NH or NR ⁶ , where R ⁶ is an alkyl group having 1 to 5 carbon atoms; In the above formula (83), R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R ⁹ is a C 1 to 10 alkylene group or arylene group having 6 to 20 carbon atoms, X ² is O, S, NH or NR ¹³ , R ¹³ is an alkyl group having 1 to 5 carbon atoms, and m is a number of 1 to 6.

When the photopolymerizable compound (A) contains a cationically polymerizable compound and the reactive functional group is a cationically polymerizable functional group, the cationically polymerizable functional group is, for example, selected from the group consisting of a cyclic ether group and a vinyl ether group. is at least one group that is The cyclic ether group is, for example, at least one of an epoxy group and an oxetane group. Organic groups with reactive functional groups are, for example, vinyl ether groups.

Among the plurality of R in the formula (80), each group (non-reactive group) other than an organic group having a reactive functional group is, for example, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group , or an organic group that does not have a reactive functional group. The organic group having no reactive functional group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. It is an alkyloxy group. The non-reactive group preferably contains one or more hydroxyl groups. In this case, the intramolecular hydrogen bond tends to improve the photostability of the ultraviolet absorber (C) itself.

A benzophenone-based reactive ultraviolet absorber has, for example, a structure represented by the following formula (90).

In the above formula (90), the multiple Rs include at least one organic group having a reactive functional group. For example, among a plurality of R, one R or each of two R is preferably an organic group having a reactive functional group.

When the photopolymerizable compound (A) contains a radically polymerizable compound and the reactive functional group is a radically polymerizable functional group, the organic group having a reactive functional group is, for example, an organic group, an organic group represented by formula (92) or an organic group represented by formula (93). In the above formula (91), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a single bond, an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms. In the above formula (92), R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, X ¹ is O, S, NH or NR ⁶ , where R ⁶ is an alkyl group having 1 to 5 carbon atoms; In the above formula (93), R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R ⁹ is a C 1 to 10 alkylene group or arylene group having 6 to 20 carbon atoms, X ² is O, S, NH or NR ¹³ , R ¹³ is an alkyl group having 1 to 5 carbon atoms, and m is a number of 1 to 6.

When the photopolymerizable compound (A) contains a cationically polymerizable compound and the reactive functional group is a cationically polymerizable functional group, the cationically polymerizable functional group is, for example, selected from the group consisting of a cyclic ether group and a vinyl ether group. is at least one group that is The cyclic ether group is, for example, at least one of an epoxy group and an oxetane group. Organic groups with reactive functional groups are, for example, vinyl ether groups.

Among the plurality of R in formula (90), each group (non-reactive group) other than an organic group having a reactive functional group is, for example, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group , or an organic group that does not have a reactive functional group. The organic group having no reactive functional group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. It is an alkyloxy group. The non-reactive groups in formula (90) preferably contain hydroxyl groups, and it is particularly preferred that at least two of the non-reactive groups are hydroxyl groups. That is, the benzophenone-based reactive ultraviolet absorber preferably has two or more hydroxyl groups. In this case, the transparency (visible light transmittance) of the cured product is less likely to be impaired, and the transmittance of light with a wavelength of 400 nm tends to be effectively reduced.

On the other hand, the non-reactive ultraviolet absorber (C2) is, for example, a benzotriazole-based ultraviolet absorber having no reactive functional group, a benzophenone-based ultraviolet absorber having no reactive functional group, or a reactive functional group. azomethine-type UV absorbers without reactive functional groups, indole-type UV absorbers without reactive functional groups, phthalocyanine-type UV absorbers with no reactive functional groups, and triazine-type UV absorbers with no reactive functional groups. contains at least one selected from the group consisting of The non-reactive UV absorber (C2) preferably contains at least one selected from the group consisting of triazine UV absorbers, benzotriazole UV absorbers, and benzophenone UV absorbers.

A benzotriazole-based ultraviolet absorber having no reactive functional group has, for example, a structure in which each of a plurality of R's is a non-reactive group in the above formula (80). In this case, each of the plurality of Rs is, for example, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, or an organic group having no reactive functional group. The organic group having no reactive functional group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. It is an alkyloxy group.

A benzophenone-based ultraviolet absorber having no reactive functional group has, for example, a structure in which each of a plurality of R's is a non-reactive group in the above formula (90). In this case, each of the plurality of Rs is, for example, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, or an organic group having no reactive functional group. The organic group having no reactive functional group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an aryl group having 6 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. It is an alkyloxy group.

The non-reactive UV absorber (C2) may contain a compound that exhibits UV absorbency when heated, ie, a so-called latent UV absorber. In this case, since the latent UV absorber does not exhibit UV absorbability in the composition (X), the composition (X) is easily cured by UV light. In addition, when the cured product is heated, the latent UV absorber in the cured product exhibits UV absorbency, making it difficult for the cured product to transmit UV rays.

When the ultraviolet absorber (C) contains a reactive ultraviolet absorber (C1) and a non-reactive ultraviolet absorber (C2), the percentage of the reactive ultraviolet absorber (C1) to the total ultraviolet absorber (C) is It is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. In this case, the UV absorber (C) is less likely to bleed out from the cured product.

The ultraviolet absorber (C) preferably contains a compound having a molecular weight of 400 or more. In this case, outgassing is less likely to occur from the cured product. The percentage of the compound having a molecular weight of 400 or more relative to the total ultraviolet absorber (C) is preferably 3% by mass or more. In this case, there is an advantage that even a thin film of 10 μm can sufficiently absorb ultraviolet rays. This percentage is more preferably 5% by mass or more, and even more preferably 8% by mass or more. Also, this percentage is preferably 30% by mass or less. In this case, there is an advantage that the composition (X) has good inkjet properties and less outgassing. This percentage is more preferably 25% by mass or less, and even more preferably 15% by mass or less.

The percentage of the ultraviolet absorber (C) is, for example, 1% by mass or more and 25% by mass or less with respect to the entire composition (X). If this percentage is 1% by mass or more, there is an advantage that the cured product is particularly difficult to transmit ultraviolet rays. This percentage is more preferably 1% by mass or more, and even more preferably 3% by mass or more. If this percentage is 25% by mass or less, there is an advantage that the coating properties of the composition (X) are good. This percentage is more preferably 20% by mass or less, and even more preferably 15% by mass or less.

The sensitizer (D) will be explained. Since the composition (X) contains the sensitizer (D), as described above, although the composition (X) contains the ultraviolet absorber (C), the composition (X) is irradiated with light. good reactivity is likely to be maintained.

The sensitizer (D) preferably contains an anthracene-based sensitizer. In this case, good reactivity is likely to be maintained even when the composition (X) is irradiated with light having a wavelength of around 395 nm. The anthracene-based sensitizer contains, for example, a compound having a structure represented by formula (70) below.

In the above formula (70), each of the plurality of R's is independently an organic group having a reactive functional group or a group other than an organic group having a reactive functional group (non-reactive group). n is a number from 1 to 6;

When a plurality of R contains an organic group having a reactive functional group, the photopolymerizable compound (A) contains a radically polymerizable compound, and the reactive functional group is a radically polymerizable functional group, the reactivity The organic group having a functional group is, for example, an organic group represented by formula (72), an organic group represented by formula (73), or an organic group represented by formula (74). In formula (72) above, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms. In the above formula (73), R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁵ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, X ¹ is O, S, NH or NR ⁶ , where R ⁶ is an alkyl group having 1 to 5 carbon atoms; In the above formula (74), R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁸ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms, and R ⁹ is a C 1 to 10 alkylene group or arylene group having 6 to 20 carbon atoms, X ² is O, S, NH or NR ¹³ , R ¹³ is an alkyl group having 1 to 5 carbon atoms, and m is a number of 1 to 6.

When the photopolymerizable compound (A) contains a cationically polymerizable compound and the reactive functional group is a cationically polymerizable functional group, the cationically polymerizable functional group is, for example, selected from the group consisting of a cyclic ether group and a vinyl ether group. is at least one group that is The cyclic ether group is, for example, at least one of an epoxy group and an oxetane group. Organic groups with reactive functional groups are, for example, vinyl ether groups.

Non-reactive groups are, for example, hydrogen atoms, halogen atoms, amino groups, cyano groups, nitro groups, or organic groups without reactive functional groups. The organic group having no reactive functional group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an aryl group having 6 to 10 carbon atoms, represented by the above formula (71). group, or a group represented by “—OR ¹⁰ ”. R ¹⁰ is an organic group having no reactive group. In the above formula (71), R ¹¹ is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkyleneoxy group having 1 to 10 carbon atoms, and R ¹² is an alkylene group having 1 to 10 carbon atoms. It is an alkyl group, an aryl group having 6 to 20 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. Each non-reactive group is particularly preferably a hydrogen atom, an OH group, a methyl group or an ethyl group. In this case, the sensitizing action of the anthracene-based sensitizer is particularly likely to be expressed, so that the good reactivity of the composition (X) is more likely to be maintained, and the need to use a large amount of sensitizer is reduced. Become.

The sensitizer (D) preferably contains an anthracene-based sensitizer (D1) having an anthracene skeleton and a group represented by “—OR ¹⁰ ” bonding to the anthracene skeleton. “—OR ¹⁰ ” is as described above. The anthracene-based sensitizer (D1) contains, for example, a compound containing at least one group in which multiple Rs are represented by "--OR ¹⁰ " in the above formula (70). When the sensitizer (D) contains the anthracene-based sensitizer (D1), the sensitization action of the sensitizer (D) is more likely to be exhibited, so that the good reactivity of the composition (X) is further maintained. Cheap. In addition, the affinity between the sensitizer (D) and the photopolymerizable compound (A) tends to be high, so even if the sensitizer (D) does not have a reactive functional group, the cured product can be sensitized. It becomes difficult for the agent (D) to bleed out.

R ¹⁰ is, for example, a saturated hydrocarbon group which may contain non-reactive groups. The non-reactive group is, for example, at least one selected from the group consisting of carbonyl groups, ether bonds, ester bonds and the like. In R ¹⁰ , the number of atoms constituting the longest linear chain bonded to O is preferably 1-10. In R ¹⁰ , the number of atoms constituting the longest linear chain bonded to O is preferably 2 or more, more preferably 4 or more, and even more preferably 5 or more. In this case, bleeding out of the sensitizer (D) is even less likely to occur. Also, the number of atoms is preferably 8 or less, more preferably 6 or less. In this case, the good reactivity of composition (X) is particularly likely to be maintained.

The anthracene-based sensitizer (D1) preferably contains, for example, a compound represented by the following formula (701). In formula (701), “—OR ¹⁰ ” is as described above. In this case, the sensitizing action of the sensitizer (D) is more likely to be exhibited, and therefore the good reactivity of the composition (X) is more likely to be maintained. In addition, the affinity between the sensitizer (D) and the photopolymerizable compound (A) tends to be high, so even if the sensitizer (D) does not have a reactive functional group, the cured product can be sensitized. It becomes difficult for the agent (D) to bleed out.

The compound represented by formula (701) is, for example, a compound represented by formula (702) below, a compound represented by formula (703) below, a compound represented by formula (704) below, and a compound represented by formula (705) below. Contains at least one selected.

The sensitizer (D) may contain compounds other than the anthracene-based sensitizer. In that case the sensitizer (D) is for example thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino ) at least one compound selected from the group consisting of benzophenone, p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde, and the like.

When the sensitizer (D) contains the anthracene-based sensitizer (D1), the percentage of the anthracene-based sensitizer (D1) to the total sensitizer (D) is preferably 50% by mass or more, It is more preferably 70% by mass or more, and even more preferably 90% by mass or more.

The percentage ratio of the sensitizer (D) to the solid content of the composition (X) is preferably 1.0% by mass or more and 4.5% by mass or less. Note that the solid content is a component excluding volatile components such as a solvent in the composition (X). If the percentage is 1.0% by mass or more, good reactivity of the composition (X) is more likely to be maintained. Further, when the percentage is 4.5% by mass or less, the transparency (visible light transmittance) of the cured product is less likely to be impaired, and outgassing generated from the sensitizer after curing can be reduced. This percentage is more preferably 1.2% by mass or more, and even more preferably 1.5% by mass or more. Also, this percentage is more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less.

Moreover, the percentage of the sensitizer (D) to the total of the ultraviolet absorber (C) and the sensitizer (D) is preferably 3% by mass or more and 70% by mass or less. When this percentage is 3% by mass or more, the good reactivity of the composition (X) is particularly likely to be maintained. Moreover, when this percentage is 70% by mass or less, the cured product becomes particularly difficult to transmit ultraviolet rays, and the storage stability of the composition (X) tends to be particularly enhanced. This percentage is more preferably 4% by mass or more, and even more preferably 5% by mass or more. This percentage is more preferably 50% by mass or less, and even more preferably 40% by mass or less.

Composition (X) may further contain a moisture absorbent (E). When the composition (X) contains the hygroscopic agent (E), the cured product of the composition (X) can have hygroscopicity. Therefore, the encapsulant 5 containing a cured product can further prevent moisture from entering the light-emitting element 4 in the light-emitting device 1 . The average particle size of the moisture absorbent (E) is preferably 200 nm or less. In this case, the cured product can have high transparency (visible light transmittance).

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

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

The zeolite particles preferably contain sodium ions. Therefore, the zeolite particles are preferably produced from at least one selected from the group consisting of A-type zeolite, X-type zeolite and Y-type zeolite. It is particularly preferred that the zeolite particles are made from 4A-type zeolite among the A-type zeolites. In these cases, the zeolite particles have a crystal structure suitable for moisture adsorption.

The pH of the zeolite particles is preferably 7 or more and 10 or less. When the pH of the zeolite particles is 7 or more, the crystals of the zeolite particles are less likely to be broken, so that the cured product of the composition (X) containing the zeolite particles can have particularly high hygroscopicity. Further, when the pH of the zeolite particles is 10 or less, the zeolite particles are less likely to inhibit curing when the composition (X) is cured. The pH of the zeolite particles was obtained by adding 0.05 g of the zeolite particles to 99.95 g of ion-exchanged water, heating the resulting dispersion at 90° C. for 24 hours, and measuring the pH of the supernatant of the dispersion with a pH measuring instrument. It is a value obtained by measuring with As a pH measuring device, for example, a compact pH meter <LAQUAtwin> B-711 manufactured by Horiba, Ltd. can be used.

The average particle diameter of the moisture absorbent (E) is preferably 10 nm or more and 200 nm or less. If this average particle size is 200 nm or less, the cured product can have particularly high transparency (visible light transmittance). Also, if the average particle size is 10 nm or more, the moisture absorbent (E) can maintain good moisture absorption. The average particle diameter is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As a measuring device, Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

The average particle diameter of the moisture absorbent (E) is preferably 150 nm or less, more preferably 100 nm or less, and particularly preferably 70 nm or less. Also, the average particle size of the moisture absorbent (E) is preferably 20 nm or more, more preferably 50 nm or more. In this case, the cured product can have particularly good transparency (visible light transmission) and hygroscopicity.

It is also preferable that the cumulative 90% diameter (D90) of the moisture absorbent (E) is 100 nm or less. In this case, the cured product can have particularly high transparency (visible light transmittance).

When the composition (X) contains the moisture absorbent (E), the percentage of the moisture absorbent (E) with respect to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. If the percentage of the hygroscopic agent (E) is 1% by mass or more, the cured product can have particularly high hygroscopicity. In addition, if the percentage of the moisture absorbent (E) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) must have a sufficiently low viscosity to the extent that it can be applied by an inkjet method. can also The percentage of the moisture absorbent (E) is more preferably 3% by mass or more, particularly preferably 5% by mass or more. Moreover, the percentage of the moisture absorbent (E) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

The composition (X) may further contain an inorganic filler other than the moisture absorbent (E). For example, composition (X) may contain nano-sized high refractive index particles. Examples of high refractive index particles include zirconia particles. When the composition (X) contains high refractive index particles, the cured product can have a high refractive index while maintaining good transparency (visible light transmittance) of the cured product. Therefore, when the cured product is applied to an optical component, it is possible to improve the extraction efficiency of light transmitted through the optical component and emitted to the outside. The average particle size of the high refractive index particles is preferably in the range of 5 to 30 nm, more preferably in the range of 10 to 20 nm.

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

When composition (X) contains moisture absorbent (E), composition (X) preferably further contains dispersant (F). In this case, the dispersant (F) can improve the dispersibility of the moisture absorbent (E) in the composition (X). Therefore, the composition (X) is less likely to have an increase in viscosity and a decrease in storage stability due to the hygroscopic agent (E).

The dispersant (F) is a surfactant that can be adsorbed on particles. The dispersing agent (F) has an adsorptive group (generally referred to as an anchor) that can be adsorbed to particles, and a molecular skeleton (generally referred to as a tail) attached to the particles by the adsorption of the adsorptive groups to the particles. The dispersant (F) includes, for example, an acrylic dispersant whose tail is an acrylic molecular chain, a urethane dispersant whose tail is a urethane molecular chain, and a polyester dispersant whose tail is a polyester molecular chain. It contains at least one component selected from the group consisting of agents. The adsorptive group includes, for example, at least one of a basic polar functional group and an acidic polar functional group. Basic polar functional groups include, for example, at least one group selected from the group consisting of amino groups, imino groups, amide groups, imide groups, and nitrogen-containing heterocyclic groups. The acidic polar functional group includes, for example, at least one group selected from the group consisting of a carboxyl group and a phosphate group. The dispersing agent (F) is, for example, Solsperse series manufactured by Nippon Ruble Resol Co., Ltd., DISPERBYK series manufactured by BYK-Chemie Japan Co., Ltd., and Ajinomoto Fine-Techno Co., Ltd. Ajinomoto Fine-Techno Co., Ltd. At least one compound selected from the group consisting of can contain

When the composition (X) contains the moisture absorbent (E), the amount of the dispersant (F) per 100 parts by mass of the moisture absorbent (E) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (F) is 5 parts by mass or more, the function of the dispersant (F) can be effectively exhibited, and when it is 60 parts by mass or less, the dispersant (F) in the cured product can be released. can be suppressed from hindering the adhesion between the cured product and the member made of an inorganic material. Further, the amount of the dispersant (F) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. .

The structure of the light emitting device 1 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 sealing material 5 and a passivation layer 6 covering the light-emitting element 4 . In this case, the light emitting element 4 is the light source, the sealing material 5 is the optical component, and the passivation layer 6 is the inorganic layer. The sealing material 5 and the passivation layer 6 overlap each other.

Light emitting element 4 includes, for example, a light emitting diode. Light-emitting diodes include, for example, at least one of organic EL elements (organic light-emitting diodes) and micro light-emitting diodes. 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. If the light emitting element 4 comprises a micro light emitting diode, the light emitting device 1 comprising 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. This light emitting device 1 is of a top emission type. The light emitting device 1 includes a support substrate 2, a transparent substrate 3 facing the support substrate 2 with a gap therebetween, a light emitting element 4 on the surface of the support substrate 2 facing the transparent substrate 3, and a passivation layer covering the light emitting element 4. 6 and encapsulant 5 .

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

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

The passivation layer 6 is preferably made of silicon nitride or silicon oxide, particularly preferably of silicon nitride. In the example shown in FIG. 1, passivation layer 6 includes first passivation layer 61 and second passivation layer 62 . The first passivation layer 61 covers the light emitting elements 4 by covering the element array 9 while being in direct contact with the element array 9 . The second passivation layer 62 is arranged on the side opposite to the element array 9 with respect to the first passivation layer 61, and a space is provided between the second passivation layer 62 and the first passivation layer 61. ing. 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 element 4 and the sealing material 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. The material of the second sealing material 52 is not particularly limited. The material of the second sealing material 52 may be the same as or different from that of the sealing material 5 .

A method for producing the sealing material 5 and a method for producing the light-emitting device 1 using the composition (X) will be described.

In the present embodiment, the encapsulant 5 is preferably produced by molding the composition (X) by an inkjet method and then curing the composition (X) by irradiating it with ultraviolet rays. In this embodiment, the composition (X) can be applied and molded by an inkjet method.

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

In the case where the composition (X) has the property of reducing the viscosity when heated, the composition (X) may be heated and then applied by an ink jet method for molding. When the viscosity of the composition (X) at 40° C. is 30 mPa·s or less, particularly 15 mPa·s or less, the viscosity of the composition (X) can be lowered by only slightly heating the composition (X). Composition (X) can be discharged by an inkjet method. The heating temperature of the composition (X) is, for example, 20°C or higher and 50°C or lower.

More specifically, for example, first, the support substrate 2 is prepared. A partition wall 7 is formed on one surface of the support substrate 2 by photolithography using, for example, a photosensitive resin material. Subsequently, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2 . The light emitting element 4 can be produced by an appropriate method such as a vapor deposition method or a coating method. In particular, it is preferable to fabricate the light-emitting element 4 by a coating method such as an inkjet method. Thus, an element array 9 is produced on the support substrate 2 .

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

Next, the composition (X) is formed on the first passivation layer 61 by, for example, an inkjet method to form a coating film. If the inkjet method is applied to both the formation of the light-emitting element 4 and the application of the composition (X), the manufacturing efficiency of the light-emitting device 1 can be particularly improved. Subsequently, the coating film of the composition (X) is cured by irradiating it with light to prepare the encapsulant 5 .

The peak wavelength of the light with which the composition (X) is irradiated is preferably around 395 nm. In the present embodiment, good curability of the composition (X) is likely to be obtained when irradiated with light having a wavelength of around 395 nm. The peak wavelength of the light with which the composition (X) is irradiated is, for example, 365 nm or more and 405 nm or less.

In irradiating the composition (X) with light, the composition (X) may be irradiated with light in an atmosphere containing oxygen such as an air atmosphere, or the composition (X) may be irradiated with light in an inert atmosphere such as a nitrogen atmosphere. may be irradiated with light. In the present embodiment, as described above, the composition (X) has an oxygen content of 75% by mass or less. Therefore, even if the photopolymerizable compound (A) contains the radical polymerizable compound (A1), oxygen Inhibition is unlikely to occur. Therefore, even if the composition (X) is irradiated with ultraviolet rays in an oxygen-containing atmosphere, the composition (X) is easily cured.

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

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

Next, the transparent substrate 3 is irradiated with ultraviolet rays from the outside. Ultraviolet rays pass through the transparent substrate 3 and reach the photocurable resin material. As a result, the photocurable resin material is cured, and the second sealing material 52 is produced.

In the present embodiment, as described above, it is possible to make it difficult for the luminous efficiency to decrease due to the passivation layer 6 and the sealing material 5 in the light emitting device 1 .

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 encapsulant 5, the light-emitting device 1 can be thinned, and the light-emitting device 1 having flexibility can be obtained. Further, in order to effectively suppress moisture to 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 8 μm or more. is even more preferable.

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, 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. is preferred.

Note that the application of the composition (X) according to this embodiment is not limited to the production of the encapsulant 5 for the light emitting element 4 . Composition (X) can be used to produce various optical components that transmit light emitted by a light source. For example, the optical component may be a color resist. That is, for example, the composition (X) may contain a phosphor, and a color resist for a color filter may be produced from the composition (X). This color filter can be provided, for example, in a display device such as an organic EL display or a micro LED display, which are light emitting devices.

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

The details of the components shown in the table are as follows. The viscosity of each component below is a value measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) under conditions of a temperature of 25° C. and a shear rate of 1000 s ⁻¹ .
-Dicyclopentanyl acrylate: Viscosity 10 mPa·s, with -RO- skeleton.
-N,N-dimethylacrylamide: manufactured by KJ Chemicals, product number DMAA, viscosity 1 mPa·s, with -RN- skeleton.
- Urethane acrylate: product number KRM9276 manufactured by Daicel Allnex, viscosity 30 mPa·s, with -RN- skeleton.
-Acryloylmorpholine: Viscosity 10 mPa·s, with -RO- skeleton and -RN- skeleton.
- Tripropylene glycol diacrylate: Viscosity 10 mPa·s, with -RO- skeleton.
- Polyethylene glycol diacrylate: Viscosity 10 mPa·s, with -RO- skeleton.
-1,9-nonanediol diacrylate: Viscosity 10 mPa·s, no -RO- skeleton and -RN- skeleton.
-VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate, viscosity 4 mPa·s, glass transition temperature 40°C, boiling point 260°C, with -RO-.
- Ditrimethylolpropane tetraacrylate: viscosity 600 mPa·s, no -RO- skeleton and -RN- skeleton.
-Celoxide 8010: manufactured by Daicel, product name Celoxide 8010, compound represented by formula (1a), viscosity 60 mPa·s, no -RO- skeleton or -RN- skeleton.
-OXT-221: 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (compound represented by formula (3)), manufactured by Toagosei Co., Ltd., product number OXT-221, viscosity 12 mP・There is s, -RO- skeleton.
-Celoxide 2021P: 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, compound represented by formula (1b), viscosity of 250 mP·s, with -RO- skeleton.
-1,2,7,8-Octanediepoxy: Viscosity 3 mP·s, no -RO- and -RN- skeletons.
-X-40-2669: Shin-Etsu Chemical Co., Ltd., product number X-40-2669, compound represented by formula (10a-1), viscosity 45 mP·s, no -RO- skeleton or -RN- skeleton.
-NBB-ME: manufactured by ENEOS Corporation, product name NBB-ME, viscosity 13 mPa·s, no -RO- skeleton or -RN- skeleton.
-AL-EOX: Yokkaichi Gosei Co., Ltd., product name AL-EOX, compound represented by formula (16) (3-allyloxymethyl-3-ethyloxetane), viscosity 2 mPa·s, with -RO- skeleton.
- Ultraviolet absorber 1: a benzotriazole-based ultraviolet reactive absorber having a cationic polymerizable functional group, represented by the following formula.

- Ultraviolet absorber 2: A benzophenone-based reactive ultraviolet absorber having two hydroxyl groups and a cationic polymerizable functional group, represented by the following chemical formula.

- Ultraviolet absorber 3: A benzophenone-based ultraviolet-reactive absorber having one hydroxyl group and a cationic polymerizable functional group, represented by the following formula.

- Ultraviolet absorber 4: A benzotriazole-based reactive ultraviolet absorber having a radically polymerizable functional group represented by the following formula.

- Ultraviolet absorber 5: A benzophenone-based reactive ultraviolet absorber having two hydroxyl groups and a radically polymerizable functional group, represented by the following formula.

- Ultraviolet absorber 6: A benzophenone-based reactive ultraviolet absorber having one hydroxyl group and a radically polymerizable functional group represented by the following formula.

- Ultraviolet absorber 7: BASF Japan Ltd., product name Tinuvin 970, a triazine-based ultraviolet absorber having no reactive functional group.
- Ultraviolet absorber 8: product number FDB-009 manufactured by Yamada Kagaku Kogyo Co., Ltd., a diazine-based ultraviolet absorber having no reactive functional group.
- Ultraviolet absorber 9: BONASORB3912 manufactured by Orient Chemical Industry Co., Ltd., an indole-based ultraviolet absorber having no reactive functional group.
- Ultraviolet absorber 10: BONASORB3701 manufactured by Orient Chemical Industry Co., Ltd., an azomethine-based ultraviolet absorber having no reactive functional group.
- Ultraviolet absorber 11: manufactured by ADEKA Corporation, product number LA-46, triazine-based ultraviolet absorber having no reactive functional group, molecular weight 512.
- Omnirad TPO H: IGM Resins B.I. V. Product name: Omnirad TPO H, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, with photobleaching property.
-CPI-210S: San-Apro Co., Ltd., product name CPI-210S, a salt of a triarylsulfonate-type cation represented by formula (64) and a (perfluoroalkyl)fluorophosphate anion.
-UVS-1331: product name Anthracure UVS-1331, manufactured by Kawasaki Kasei Co., Ltd., an anthracene-based sensitizer represented by formula (701) in which all R ¹⁰ are n-butyl groups.
-UVS-107: manufactured by Kawasaki Kasei Co., Ltd., trade name Anthracure UVS-107, an anthracene-based sensitizer represented by formula (701) in which all R ¹⁰ are isopropyloxycarbonylmethylene.

2. Evaluation Tests The following evaluation tests were conducted for Examples and Comparative Examples. The results are shown in the table.

(1) Viscosity The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, Model No. DHR-2) under conditions of a temperature of 25° C. and a shear rate of 1000 s ⁻¹ .

(2) Curability (395 nm)
An IR spectrum was obtained by measuring the composition with an infrared spectrometer (manufactured by Agilent Technologies, Model No. Agilent Cary 610 FTIR microscope system).

The composition was applied to prepare a coating film having a thickness of 10 μm, and the coating film was exposed to light with a peak wavelength of 395 nm using a UV irradiator (manufactured by Ushio Inc., model number E075IIHD) at an irradiation intensity of 3 W/cm ² and an integrated light amount. Irradiation was performed under the condition of 0.9 J/cm ² . Subsequently, an IR spectrum was obtained by measuring the composition (cured product) after being irradiated with ultraviolet rays with the above infrared spectroscopic analyzer.

The absorption peak intensity of the reactive functional group was measured in each of the two IR spectra. Before and after UV irradiation using the formula { _1- ( _{I0 -} I1)/ _I0 }×100(%) from the peak intensity _I0 of the coating film and the peak intensity I1 of the cured product. The reduction rate of reactive functional groups in the composition at was calculated. The result was taken as the reaction rate.

The absorption of the reactive functional group means the absorption of the alicyclic epoxy group appearing at 885 cm ^-1 in Examples 1 to 16 and Comparative Examples 1 and 2, and at 810 cm ^-1 in Examples 17 to 36 and Comparative Example 3. is the absorption of the acryloyl group appearing in .

The results were evaluated as follows.
A: 90% or more.
B: 80% or more and less than 90% C: less than 80%.

(3) Inkjet properties The composition was placed in a cartridge of an inkjet printer (model DMP2831, manufactured by Fujifilm), and droplets of the composition were ejected from the nozzle of the inkjet printer at a temperature of 30°C and a frequency of 1 kHz. This droplet was observed with a high-speed camera and evaluated as follows. As a result, "A" indicates the case where the droplet does not separate, "B" indicates the case where the satellite separates from the original droplet and then unites with the original droplet to become one droplet again, and "B" indicates the original droplet. A case where the satellite was separated from the droplet and was not integrated was evaluated as "C".

(4) Glass transition temperature A coating film is prepared by applying the composition, and this coating film is exposed to light with a peak wavelength of 395 nm using a UV irradiator (manufactured by Ushio Inc., model number E075IIHD) in an air atmosphere. The coating film was photo-cured by irradiation under the conditions of an irradiation intensity of 3 W/cm ² and an integrated light quantity of 1.5 J/cm ² to prepare a film having a thickness of 500 μm. The glass transition temperature of a sample cut out from this film was measured using a viscoelasticity measuring device (manufactured by Hitachi High-Tech Science, model number DMA7100).

(5) Transmittance A coating film is prepared by applying the composition, and the coating film is exposed to light with a peak wavelength of 395 nm using a UV irradiation device (manufactured by Ushio Inc., model number E075IIHD) with an irradiation intensity of 3 W / cm. ² and an integrated light amount of 1.5 J/cm ² , the coating film was photocured to prepare a film having a thickness of 15 μm.

The transmittance of light at wavelengths of 430 nm and 400 nm of this film was measured using a spectrophotometer (manufactured by Nippon Denshoku Industries Co., Ltd., model number SD7000).

(6) Bleed-out evaluation A coating film was prepared by applying the composition, and the coating film was irradiated with light having a peak wavelength of 395 nm using a UV irradiation device (manufactured by Ushio Inc., model number E075IIHD) at an irradiation intensity of 3 W/ The coating film was photo-cured by irradiating under the conditions of 1.5 J/cm ² of cumulative light quantity and cm ² to produce a film having a thickness of 15 μm. The obtained film was exposed for 500 hours under conditions of 85° C. and 85% by mass relative humidity, and then the film was visually observed. A case where spots were observed was evaluated as B, and a case where spots were confirmed as a whole was evaluated as C.

(7) Outgassing Evaluation The outgassing when the cured product of the composition was heated was sampled by the headspace method and measured by gas chromatography. Specifically, 100 mg of the composition was first placed in a 22 mL headspace vial. Subsequently, the composition was irradiated with light having a peak wavelength of 395 nm in an air atmosphere using a UV irradiator (manufactured by Ushio Inc., model number E075IIHD) at an irradiation intensity of 3 W/cm ² and an integrated light intensity of 1.5 J/cm ² . After the composition was cured by irradiation under conditions, the vial was sealed. The composition was then heated at 100° C. for 30 minutes before introducing the vapor phase portion of the vial into a gas chromatograph for analysis. As a result, the concentration of outgas generated from the composition was specified based on the peak area of the obtained gas chromatogram. Outgassing concentration is the volume fraction of outgassing in the vapor phase of the vial relative to the volume of the vial (22 mL).

Note that the concentration of outgas was specified using toluene as a reference substance. Specifically, two reference samples with toluene concentrations of 1000 ppm and 100 ppm were prepared by volatilizing toluene in a vial. Each reference sample was introduced into the gas chromatograph and analyzed. From the peak areas of the two chromatograms thus obtained, the relationship between the peak area and the concentration was defined, and based on this result, the outgassing concentration was specified.

The results were evaluated as follows.
A: Concentration of 200 ppm or less.
B: Concentration more than 200 ppm and less than or equal to 300 ppm.
C: Concentration over 300 ppm.

(8) Storage property The composition was stored at 60°C for 336 hours. As a result, "A" when there is no change in the color and viscosity of the composition, "B" when at least one of yellowing and gelation is confirmed in the composition, and the composition hardens after storage. "C" was evaluated in the case where it had disappeared.

(9) Device Evaluation A 30 mm square glass substrate (700 μm thick) with an ITO electrode was washed with acetone and isopropanol. After that, the following compounds were sequentially deposited by a vacuum deposition method so as to form a thin film, and an organic EL element of 2 mm square consisting of an anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode was obtained. got the substrate. The structure of each layer is as follows.
・Anode: ITO, film thickness of anode: 150 nm
・Hole injection layer 4,4′,4″-tris{2-naphthyl(phenyl)amino}triphenylamine (2-TNATA)
・Hole transport layer N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD)
Emitting Layer Tris(8-hydroxyquinolinato)aluminum (metal complex material), the film thickness of the emitting layer is 1000 Å, and the emitting layer also functions as an electron transport layer.
・Electron injection layer lithium fluoride ・Cathode aluminum film thickness 150 nm
After that, a mask (cover) having an opening of 10 mm×10 mm was placed so as to cover the organic EL element of 2 mm×2 mm, and a SiN film was formed by plasma CVD.

Next, the composition was applied to a thickness of 10 μm so as to cover a 2 mm×2 mm organic EL element using an inkjet device in a nitrogen atmosphere, with a peak wavelength of 395 nm, an irradiation intensity of 3 W/cm ² and an integrated light amount of 1.5 J. This composition was cured under the condition of 1/cm ² . Thus, a sealing material was produced.

Subsequently, a mask (cover) having an opening of 10 mm×10 mm was placed so as to cover the entire sealing material, and a SiN film was formed by plasma CVD.

The thickness of the formed SiN film (inorganic film) was about 1 μm. After that, the SiN film is attached to a 30 mm × 30 mm × 0.7 mmt alkali-free glass (Eagle XG manufactured by Corning) using a 30 mm × 30 mm × 25 µmt transparent double-sided tape without a base material to produce an organic EL light emitting device. did.

The organic EL light-emitting device immediately after being produced was exposed for 70 hours under conditions of 85° C. and relative humidity of 85% by mass, and then a voltage of 6 V was applied, and the light emitting state of the organic EL element was observed visually and with a microscope, The dark spot diameter was measured.

The diameter of the dark spot can be regarded as an index for evaluating the extent to which the sealing material permeates into the pinholes of the passivation layer and the extent to which moisture in the sealing material is discharged as outgassing. The diameter of the dark spots was evaluated as "C" when more than 50 μm and 300 μm or less, "B" when 50 μm or less, and "A" when no dark spots were present.

(10) Device evaluation (Sunshine weather meter)
A light resistance evaluation test of the device prepared in (9) above was performed using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd., model number S80HB) with an integrated light intensity of 236 W / m2, a black panel temperature of 63 ° C., and a test time of 400 hours. I did it on condition. As a result, the luminance of the device was evaluated as "A" when it was 90% or more compared to the initial luminance, "B" when it was 80% or more and less than 90%, and "C" when it was less than 80%.

Claims (20)

Containing a photopolymerizable compound (A), a photopolymerization initiator (B), an ultraviolet absorber (C), and a sensitizer (D),
The photopolymerizable compound (A) contains a monofunctional photopolymerizable compound (A011),
The percentage of the monofunctional photopolymerizable compound (A011) to the solid content is 10% by mass or more and 40% by mass or less.
A photocurable resin composition. The photopolymerizable compound (A) further contains a polyfunctional photopolymerizable compound (A012),
The percentage of the polyfunctional photopolymerizable compound (A012) to the solid content is 50% by mass or more.
The photocurable resin composition according to claim 1. The UV absorber (C) includes a benzotriazole UV absorber, a benzophenone UV absorber, an azomethine UV absorber, an indole UV absorber, a diazine UV absorber, a triazine UV absorber, and a pyrazolidinedione. containing at least one selected from the group consisting of a UV absorber and an ethylene UV absorber,
The photocurable resin composition according to claim 1 or 2. The sensitizer (D) contains an anthracene-based sensitizer,
The photocurable resin composition according to claim 1 or 2. The anthracene-based sensitizer contains an anthracene-based sensitizer (D1) having an anthracene skeleton and a group represented by —OR ¹⁰ bonding to the anthracene skeleton,
R ¹⁰ is an organic group having no reactive group, and the number of atoms constituting the longest linear chain bonded to O in R ¹⁰ is 1 to 10.
The photocurable resin composition according to claim 4. A coating film having a thickness of 10 μm was prepared from the photocurable resin composition, and the coating film was irradiated with light having a peak wavelength of 395 nm under the conditions of an irradiation intensity of 3 W / cm ² and an integrated light amount of 0.9 J / cm ² . , the reaction rate of the photopolymerizable compound (A) is 80% or more,
The photocurable resin composition according to any one of claims 1 to 5. A cured product having a thickness of 10 μm obtained by curing the photocurable resin composition has a transmittance of 30% or less for light having a wavelength of 400 nm.
The photocurable resin composition according to any one of claims 1 to 6. A cured product having a thickness of 10 μm obtained by curing the photocurable resin composition has a transmittance of 70% or more for light having a wavelength of 430 nm.
The photocurable resin composition according to claim 7. The ratio of outgassing generated when the cured product of the photocurable resin composition is heated at 100 ° C. for 30 minutes is 300 ppm or less.
The photocurable resin composition according to any one of claims 1 to 8. The photopolymerizable compound (A) contains a radically polymerizable compound,
The photopolymerization initiator (B) contains a photopolymerization initiator (B1) having photobleaching properties.
The photocurable resin composition according to any one of claims 1 to 9. The photopolymerization initiator (B1) contains an acylphosphine oxide photopolymerization initiator.
The photocurable resin composition according to claim 10. The photopolymerizable compound (A) contains a cationic polymerizable compound,
The photopolymerization initiator (B) contains a salt having a (perfluoroalkyl)fluorophosphate anion,
The photocurable resin composition according to any one of claims 1 to 9. The glass transition temperature of the cured product is 75 ° C. or higher,
The photocurable resin composition according to any one of claims 1 to 12. At least one of the viscosity at 25 ° C. and the viscosity at 40 ° C. is 30 mPa s or less,
The photocurable resin composition according to any one of claims 1 to 13. Molded by being ejected by the inkjet method,
The photocurable resin composition according to any one of claims 1 to 14. for making an optical component that transmits light emitted by a light source,
The photocurable resin composition according to any one of claims 1 to 15. Including a cured product of the photocurable resin composition according to any one of claims 1 to 16,
optics. After molding the photocurable resin composition according to any one of claims 1 to 16 by an inkjet method, the photocurable resin composition is irradiated with light and cured,
A method of manufacturing an optical component. A light source and an optical component that transmits light emitted by the light source, the optical component comprising a cured product of the photocurable resin composition according to any one of claims 1 to 16,
Luminescent device. A method for manufacturing a light-emitting device comprising a light source and an optical component that transmits light emitted by the light source,
manufacturing the optical component by the method of claim 18,
A method for manufacturing a light-emitting device.

Images