CN114316650A

CN114316650A - Ultraviolet-curable resin composition, optical component, method for producing optical component, light-emitting device, and method for producing light-emitting device

Info

Publication number: CN114316650A
Application number: CN202111147228.XA
Authority: CN
Inventors: 池上裕基; 浦冈祐辅; 千秋孝弘
Original assignee: Panasonic Intellectual Property Management Co Ltd
Current assignee: Panasonic Intellectual Property Management Co Ltd
Priority date: 2020-09-29
Filing date: 2021-09-28
Publication date: 2022-04-12
Also published as: JP2022056388A

Abstract

The invention provides an ultraviolet-curable resin composition which is not easy to generate stripe-shaped concave-convex on the surface of a cured product when the cured product is prepared by irradiating ultraviolet rays and curing. The ultraviolet-curable resin composition contains a photopolymerizable compound (A) and a photopolymerization initiator (B). A coating film having a thickness of 10 μm was formed from the ultraviolet-curable resin composition and irradiated at an intensity of 7W/cm²And the accumulated light amount is 2.1J/cm²Under the conditions of curing shrinkage when the coating film is irradiated with ultraviolet rays having a wavelength region of a peak wavelength of 385 to 405nm and at an irradiation intensity of 3W/cm²And the accumulated light amount is 0.9J/cm²The absolute value of the difference in cure shrinkage rate in the case of the conditional irradiation of (3) is 2 percentage points or less.

Description

Ultraviolet-curable resin composition, optical component, method for producing optical component, light-emitting device, and method for producing light-emitting device

Technical Field

The present invention relates to an ultraviolet-curable 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 an ultraviolet-curable resin composition containing a photopolymerizable compound and a photopolymerization initiator, an optical component produced from the ultraviolet-curable resin composition, a method for producing an optical component using the ultraviolet-curable resin composition, a light-emitting device including the optical component, and a method for producing a light-emitting device using the ultraviolet-curable resin composition.

Background

In a light-emitting device including a light-emitting element such as an organic EL element as a light source, for example, the organic EL element is disposed on a support substrate, a transparent substrate is disposed so as to face the support substrate, and a transparent sealing material is filled between the support substrate and the transparent substrate. The sealing material is produced by, for example, an ink jet method.

For example, International publication No. 2018/074506 discloses a sealing agent for an organic EL display device, which comprises a polymerizable compound and a polymerization initiator, and has a viscosity at 25 ℃ of 5 to 50 mPas, a surface tension at 25 ℃ of 15 to 35mN/m, and a Poisson's ratio at 25 ℃ of a cured product of 0.28 to 0.40 (see claim 1 of International publication No. 2018/074506).

Disclosure of Invention

Problems to be solved by the invention

According to the studies of the inventors, when a cured product is produced by irradiating an ultraviolet-curable resin composition with ultraviolet rays and curing the composition, streaky irregularities may be formed on the surface of the cured product. In particular, when a coating film of an ultraviolet-curable resin composition is cured by moving an irradiation position while ultraviolet rays are irradiated from a light-emitting diode to the surface of the coating film, streaky unevenness is likely to occur. Such unevenness deteriorates the light emission characteristics of the light emitting device.

The present invention addresses the problem of providing an ultraviolet-curable resin composition that, when a cured product is produced by curing the cured product by irradiation with ultraviolet light, is less likely to produce streaky irregularities on the surface of the cured product, an optical component produced from the ultraviolet-curable resin composition, a method for producing an optical component using the ultraviolet-curable resin composition, a light-emitting device provided with the optical component, and a method for producing a light-emitting device using the ultraviolet-curable resin composition.

Means for solving the problems

An ultraviolet-curable resin composition according to one embodiment of the present invention contains a photopolymerizable compound (a) and a photopolymerization initiator (B). A coating film having a thickness of 10 μm was formed from the above ultraviolet-curable resin composition, and the irradiation intensity was 7W/cm²And the accumulated light amount is 2.1J/cm²Under the conditions of curing shrinkage when the coating film is irradiated with ultraviolet rays having a wavelength region of any wavelength from 385 to 405nm at a peak wavelength and irradiation intensity of 3W/cm²And the accumulated light amount is 0.9J/cm²Under the condition (3), the absolute value of the difference in curing shrinkage rate when the ultraviolet ray is irradiated is 2% or less.

An optical component according to an embodiment of the present invention includes a cured product of the ultraviolet-curable resin composition.

A method for manufacturing an optical component according to an embodiment of the present invention includes: after the ultraviolet curable resin composition is molded by an ink jet method, the ultraviolet curable resin composition is irradiated with ultraviolet rays and cured.

A light-emitting device according to one embodiment of the present invention includes a light source and an optical member that transmits light emitted from the light source, and the optical member includes a cured product of the ultraviolet-curable 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 member that transmits light emitted from the light source, and includes a step of manufacturing the optical member by the method for manufacturing an optical member.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one embodiment of the present invention, there can be provided an ultraviolet-curable resin composition which is less likely to cause streak-like irregularities on the surface of a cured product when the cured product is produced by curing the cured product by irradiation with ultraviolet light, an optical component produced from the ultraviolet-curable resin composition, a method for producing an optical component using the ultraviolet-curable resin composition, a light-emitting device provided with the optical component, and a method for producing a light-emitting device using the ultraviolet-curable resin composition.

Drawings

Fig. 1 is a schematic cross-sectional view showing a first example of a light-emitting device according to an embodiment of the present invention.

Detailed Description

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

The ultraviolet-curable resin composition (hereinafter also referred to as composition (X)) of the present embodiment contains a photopolymerizable compound (a) and a photopolymerization initiator (B). A coating film having a thickness of 10 μm was formed from the composition (X) at an irradiation intensity of 7W/cm²And the accumulated light amount is 2.1J/cm²Under the conditions (3) that the coating film is irradiated with ultraviolet light having a peak wavelength of 385 to 405nm in an arbitrary wavelength range, the curing shrinkage ratio (hereinafter, also referred to as the first curing shrinkage ratio) and the irradiation intensity are set to 3W/cm²And the accumulated light amount is 0.9J/cm²The absolute value of the difference in the curing shrinkage ratio (hereinafter, also referred to as the second curing shrinkage ratio) when irradiated under the condition(s) of (2) or less percentage points (hereinafter, also referred to as the curing shrinkage ratio difference).

In the present embodiment, if the difference between the first curing shrinkage rate and the second curing shrinkage rate can be achieved by 2% or less when ultraviolet light having a certain wavelength in a wavelength region having a peak wavelength of 385nm to 405nm is used, the difference between the first curing shrinkage rate and the second curing shrinkage rate cannot be achieved by 2% or less when ultraviolet light having a peak wavelength of another wavelength in the wavelength region is used. In the case of using ultraviolet rays having a peak wavelength of 395nm, it is particularly preferable if the difference between the first curing shrinkage and the second curing shrinkage can be achieved to 2% or less. It is also preferable that the difference between the first curing shrinkage and the second curing shrinkage is 2 percentage points or less even in any wavelength region having a peak wavelength of ultraviolet light of 385nm to 405 nm.

According to the present embodiment, when a cured product is produced by irradiating the composition (X) with ultraviolet light, streaky irregularities are less likely to occur on the surface of the cured product. This is considered to be because the absolute value of the difference between the first cure shrinkage and the second cure shrinkage of the composition (X) is small, and thus a local difference in shrinkage is unlikely to occur when the composition (X) is cured, that is, the composition (X) is likely to uniformly shrink as a whole.

In particular, when a coating film of an ultraviolet-curable resin composition is cured by moving an irradiation position of ultraviolet rays while irradiating the surface of the coating film with ultraviolet rays from a light-emitting diode, portions of the coating film where the irradiation amount of ultraviolet rays is relatively high tend to be generated along a linear trajectory of the irradiation position of ultraviolet rays, and portions where the irradiation amount of ultraviolet rays is relatively low tend to be generated between the portions. Therefore, generally, streaky unevenness is likely to occur in the cured product of the coating film due to the difference in curing shrinkage between the above portions. However, in the present embodiment, as described above, since the absolute value of the difference between the first cure shrinkage ratio and the second cure shrinkage ratio of the composition (X) is small, even if a difference in the irradiation amount of ultraviolet light locally occurs in the coating film of the composition (X), the difference in the shrinkage amount is unlikely to occur, and it is estimated that unevenness is unlikely to occur in the cured product.

The absolute value of the difference between the first curing shrinkage and the second curing shrinkage is more preferably 1.5 percentage points or less, and still more preferably 1 percentage point or less. The smaller the value, the more preferable the value is, and 0 percentage point is desirable. Specific measurement methods and measurement conditions for the first cure shrinkage and the second cure shrinkage of the composition (X) are described in detail in the column of examples described later.

A coating film having a thickness of 10 μm was prepared from the composition (X), and the irradiation intensity was 3W/cm²And the accumulated light amount is 0.9J/cm²When ultraviolet light having a peak wavelength of 395nm is irradiated to the coating film, the reaction rate of the photopolymerizable compound (a) in the composition (X) is preferably 80% or more. In this case, even if the composition (X) is irradiated with ultraviolet rays and cured, a difference in the amount of ultraviolet rays locally occurs, and a difference in the reactivity of the photopolymerizable compound (a) does not easily occur in the cured product. Thus, in combination withSince the difference in shrinkage is particularly unlikely to occur during curing of the substance (X), unevenness is unlikely to occur in the cured product. Such characteristics of the composition (X) can be achieved by improving the reactivity of the photopolymerizable compound (a) by the composition of the composition (X) described later. The reduction rate of the reactive functional groups in the photopolymerizable compound (a) is defined as the reaction rate of the photopolymerizable compound (a), and is obtained from the result of analyzing the composition (X) by infrared spectroscopy before and after irradiation with ultraviolet light. An example of a specific method for determining the reaction rate is described in the following example column.

An optical member can be produced from the composition (X), and a light-emitting device provided with the optical member 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).

The composition (X) is preferably formed by an ink-jet method. In this case, the cured product of the composition (X) can be easily produced with high positional accuracy. In addition, when the composition (X) is molded by an ink jet method, foreign matter is less likely to be mixed into the composition (X) and its cured product, and thus the yield in producing an optical component is less likely to be deteriorated, as compared with the case of molding by a printing method accompanied by contact, such as a screen printing method.

At least one of the viscosity at 25 ℃ and the viscosity at 40 ℃ of the composition (X) is preferably 30 mPas or less.

When the viscosity of the composition (X) at 25 ℃ is 30mPa · s or less, the composition (X) can be easily molded at room temperature, and particularly can be easily molded by an ink jet method. The viscosity is more preferably 25 mPas or less, still more preferably 20 mPas or less, and particularly preferably 15 mPas or less. The viscosity is also preferably 1mPa · s or more, and more preferably 5mPa · s or more.

When the viscosity of the composition (X) at 40 ℃ is 30 mPas or less, the viscosity can be reduced by slightly heating the composition (X) regardless of the viscosity of the composition (X) at room temperature. Therefore, if heating is performed, the composition (X) can be easily molded, and particularly can be easily molded by an ink jet method. Further, since the viscosity of the composition (X) can be reduced without heating the composition (X) to a large extent, the composition of the composition (X) is less likely to change due to volatilization of components in the composition (X). The viscosity is more preferably 25 mPas or less, still more preferably 20 mPas or less, and particularly preferably 15 mPas or less. The viscosity is also preferably 1mPa · s or more, and more preferably 5mPa · s or more.

The low viscosity of such a composition (X) at 25 ℃ or 40 ℃ can be achieved by the composition of the composition (X) as specified below. The method and conditions for measuring the viscosity of the composition (X) at 25 ℃ and 40 ℃ are described in detail in the column of examples described later.

The proportion of outgas generated when a cured product of the composition (X) is heated at 80 ℃ for 30 minutes is preferably 500ppm or less. In this case, the outgas is unlikely to be generated from the cured product. Therefore, for example, voids due to outgas are not easily generated in a light-emitting device including an optical member including a cured product. Therefore, water and oxygen do not easily reach the light-emitting element through the void, and the light-emitting element is not easily deteriorated by water and oxygen.

The composition (X) preferably contains no solvent or a solvent in an amount of 1 mass% or less. In this case, the composition (X) and the cured product of the composition (X) are less likely to generate outgas from the solvent. In addition, a drying step for removing the solvent from the composition (X) and the cured product may not be required in the production of the optical member and the light-emitting device. In this case, at least one of the heating temperature and the heating time in the drying step can be reduced. Therefore, the outgas can be hardly generated from the optical member without lowering the manufacturing efficiency of the optical member and the light-emitting device. In particular, in the case where the composition (X) is molded by an ink jet method, the thickness of the optical member is less likely to be reduced because the solvent is volatilized from the molded composition (X). Therefore, the thickness of the optical member can be ensured as much as possible while molding by an ink jet method. The content of the solvent is more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferred that composition (X) contains no solvent or only an inevitably incorporated solvent.

The glass transition temperature of the cured product of the composition (X) is preferably 80 ℃ or higher. That is, the composition (X) preferably has a property of being cured into a cured product having a glass transition temperature of 80 ℃ or higher. In this case, the cured product can have good heat resistance. Therefore, for example, when a cured product is subjected to a treatment involving a temperature increase, the cured product is less likely to deteriorate. Therefore, for example, in the case where a layer of an inorganic material (for example, the passivation layer 6) is formed by a vapor deposition method such as a plasma CVD method, the optical member is less likely to be deteriorated even if the optical member is heated. Further, by improving the heat resistance, the optical member can be adapted to the vehicle-mounted application in which the requirement for heat resistance is strict. The glass transition temperature of the cured product is more preferably 90 ℃ or higher, and still more preferably 100 ℃ or higher. The glass transition temperature of the cured product can be achieved by the composition of the composition (X) described in detail below.

The volatility in the case of heat-treating 20mg of the composition (X) at 100 ℃ for 30 minutes by using a thermogravimetric analyzer is preferably 40% or less. The volatility of the composition (X) is defined as the percentage of the weight reduction of the composition (X) after treatment (difference between the weight of the composition (X) before treatment and the weight of the composition (X) after treatment) with respect to the weight of the composition (X) before treatment. In this case, since the volatility of the composition (X) is low, the storage stability of the composition (X) can be improved. Further, it is difficult to generate outgas from the cured product of the composition (X) and the optical member. Therefore, it is more difficult to generate voids caused by the outgas in the light-emitting device. The volatility of the composition (X) can be determined by subjecting 20mg of the composition (X) to a heat treatment at 100 ℃ for 30 minutes using a thermogravimetric analyzer and calculating the weight loss of the weight after the treatment relative to the weight before the treatment. The volatility when 20mg of the composition (X) is heat-treated at 100 ℃ for 30 minutes by using a thermogravimetric analyzer is more preferably 30% or less, and still more preferably 20% or less. The lower limit of the volatility of the composition (X) is not particularly limited, and may be, for example, 0.1% or more.

The components contained in the composition (X) will be described in more detail.

The photopolymerizable compound (a) is a component capable of undergoing a polymerization reaction upon irradiation with ultraviolet rays in the presence or absence of the photopolymerization initiator (B). The photopolymerization initiator (B) may contain a curing catalyst. The photopolymerizable compound (a) contains, for example, at least one component selected from the group consisting of monomers, oligomers, and prepolymers.

The photopolymerizable compound (a) contains at least one of a radical polymerizable compound (a1) and a cation polymerizable compound (a2), for example. When the photopolymerizable compound (a) contains the radical polymerizable compound (a1), the photopolymerization initiator (B) preferably contains a photoradical polymerization initiator (B1). When the photopolymerizable compound (a) contains the cationically polymerizable compound (a2), the photopolymerization initiator (B) preferably contains a photo cationic polymerization initiator (B2) (cationic curing catalyst).

The case where the photopolymerizable compound (a) contains the radical polymerizable compound (a1) will be described.

The radically polymerizable compound (a1) preferably contains an acrylic compound (Y). The acrylic compound (Y) has one or more (meth) acryloyl groups in one molecule.

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

The viscosity of the whole acrylic compound (Y) at 40 ℃ is preferably 50 mPas or less. In this case, the acrylic compound (Y) can particularly reduce the viscosity of the composition (X) when heated. The viscosity of the entire acrylic compound (Y) is more preferably 30mPa · s or less, and particularly preferably 20mPa · s or less. The viscosity of the entire acrylic compound (Y) is, for example, 3mPa · s or more.

The percentage of components having a boiling point of 270 ℃ 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 less likely to be impaired, and outgas is particularly less likely to be generated from the cured product. The percentage of the component having a boiling point of 280 ℃ or higher in the acrylic compound (Y) is more preferably 80% by mass or higher.

The acrylic compound (Y) preferably contains a component having a viscosity of 20 mPas or less at 25 ℃. In this case, the viscosity of the composition (X) can be reduced.

The proportion of the component having a viscosity of 20 mPas or less at 25 ℃ to the total amount of the acrylic compound (Y) is preferably 50 to 100% by mass. In this case, the viscosity of the composition (X) can be particularly reduced, and the composition (X) can be applied particularly easily by an ink jet method. The proportion is more preferably 60% by mass or more, and still more preferably 70% by mass or more. The ratio is still more preferably 95% by mass or less, and still more preferably 90% by mass or less.

The component having a viscosity at 25 ℃ of 20 mPas or less preferably contains a compound having a glass transition temperature of 80 ℃ or more. In this case, the viscosity of the composition (X) can be reduced, and the glass transition temperature of the cured product can be increased. The component preferably contains a compound having a glass transition temperature of 90 ℃ or higher, and more preferably contains a compound having a glass transition temperature of 100 ℃ or higher. The upper limit of the glass transition temperature of the compound contained in the component is not limited, and is, for example, 150 ℃ or lower.

The compounds that the acrylic compound (Y) may contain are explained.

The acrylic compound (Y) preferably contains a polyfunctional acrylic compound (Y1) having two or more radically polymerizable functional groups containing a (meth) acryloyl group in one molecule. In this case, the polyfunctional acrylic compound (Y1) can increase the glass transition temperature of the cured product, and therefore, the heat resistance of the cured product can be improved. The proportion of the polyfunctional acrylic compound (Y1) is preferably 50 mass% or more and 100 mass% or less with respect to the whole acrylic compound (Y). The acrylic compound (Y) may contain only the polyfunctional acrylic compound (Y1).

The polyfunctional acrylic compound (Y1) may contain, for example, a compound selected from the group consisting of 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol oligoacrylate, diethylene glycol diacrylate, 1, 6-hexanediol oligoacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, pentaerythritol tetraacrylate, propoxylated (2) neopentyl glycol diacrylate, trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol triacrylate, ethoxylated (3) trimethylolpropane triacrylate, poly (2-hydroxyethyl) isocyanurate triacrylate, poly (1-co-hydroxyethyl) acrylate, poly (meth) acrylate, and poly (meth) acrylate, and poly (meth) acrylate), and poly (meth) acrylate, Propoxylated (3) glycerol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated (4) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, hexanediol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol triacrylate, dipentaerythritol 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, propylene glycol acrylate, propylene glycol diacrylate, propylene glycol acrylate, propylene glycol diacrylate, propylene glycol acrylate, propylene glycol, Hydroxypivalic acid neopentyl glycol diacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphoric acid triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, pentaerythritol diacrylate, and/acrylate, pentaerythritol diacrylate, and the like, At least one compound selected from the group consisting of propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate and 2- (2-ethyleneoxyethoxy) ethyl acrylate.

The acrylic equivalent of the polyfunctional acrylic compound (Y1) is preferably not more than 150g/eq, more preferably not less than 90g/eq and not more than 150 g/eq. The weight average molecular weight of the polyfunctional acrylic compound (Y1) is, for example, 100 or more and 1000 or less, and more preferably 200 or more and 800 or less.

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

CH₂＝CR¹-COO-(R³-O)n-CO-CR²＝CH₂…(200)

In the formula (200), R¹And R²Each is hydrogen or methyl, n is an integer of 1 or more, R³Is an alkylene group having 1 or more carbon atoms, and when n is 2 or more, a plurality of R's in one molecule³May be the same or different from each other.

The compound (Y11) has a structure represented by the formula (200), particularly R of the formula (200)³Has 3 or more carbon atoms, and thus it is difficult to improve the affinity of the cured product with water. R³The number of carbon atoms of (b) is, for example, 1 to 15, preferably 3 to 15. Further, the compound (Y11) having the structure represented by formula (200) and particularly having two (meth) acryloyl groups in one molecule can increase the glass transition temperature of the cured product, and therefore can improve the heat resistance of the cured product. Further, of the formula (200)n is an integer of 1 to 12 inclusive, for example.

The percentage of the compound (Y11) to the acrylic compound (Y) is preferably 50% by mass or more. In this case, the affinity of the cured product for water is not particularly easily improved. The percentage of the compound (Y11) to the acrylic compound (Y) is, for example, 100 mass% or less, or 95 mass% or less, preferably 80 mass% or less.

The compound (Y11) particularly preferably contains a component having a boiling point of 270 ℃ 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 ℃ or higher. In this case, the acrylic compound (Y) is less likely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Even if the compound (Y11) remains unreacted in the cured product of the composition (X), the outgas generated by the compound (Y11) is less likely to be generated from the cured product. Therefore, voids due to the outgassed gas are less likely to be generated in the light-emitting device 1. If there is a void in the light-emitting device 1, moisture may enter the light-emitting element 4 through the void, and if the void is not easily generated, moisture does not easily enter the light-emitting element 4. The boiling point is a boiling point at normal pressure obtained by converting a boiling point under reduced pressure, and can be obtained, for example, by a method shown in Science of Petroleum, vol.ii.p.1281 (1938). More preferably, the compound (Y11) contains a component having a boiling point of 280 ℃ or higher.

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

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

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

The alkylene glycol di (meth) acrylate is a compound in which n is 1 in the formula (200). In this case, R in the formula (200)³The number of carbon atoms of (C) is preferably 4 to 12. R³The polymer may be linear or branched. In particular, the alkylene glycol di (meth) acrylate preferably contains at least one compound selected from the group consisting of 1, 4-butanediol diacrylate, 1, 3-butanediol diacrylate, neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 9-nonanediol diacrylate, 1, 10-decanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 3-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1, 6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, and 1, 12-dodecanediol dimethacrylate. The alkylene glycol di (meth) acrylate preferably contains a monomer selected from the group consisting of SR213, product No. V195, product No. SR212, product No. SR247, product No. SR238, product No. LIGHT ACRYLATE NP-A, Sartomer, product No. SR238NS, product No. V230, product No. HDDA, product No. 1, 6HX-A manufactured by Coronze chemical industry, product No. V260 manufactured by Osaka organic chemical industry, product No. 1, 9-ND-A manufactured by Coronze chemical industry, product No. A-NOD-A, Sartomer manufactured by Newzhongcun chemical industry, product No. CD595 manufactured by Sartomer, product No. SR214NS manufactured by Sartomer, product No. BD manufactured by Newzhongcun chemical industry, and product No. BD manufactured by Sartomer.SR297, product No. SR248 from Sartomer, product No. LIGHT ESTER NP from Cogrong chemical industry, product No. SR239NS from Sartomer, product No. LIGHT ESTER 1, 6HX from Cogrong chemical industry, product No. HD-N from Newzhongmura chemical industry, product No. LIGHT ESTER 1, 9ND from Cogrong chemical industry, product No. NOD-N from Newzhongmura chemical industry, product No. LIGHT ESTER 1, 10DC from Cogrongmura chemical industry, product No. DOD-N from Newzhongmura chemical industry, and product No. SR262 from Sartomer.

The polyalkylene glycol di (meth) acrylate is, for example, a compound of the formula (200) wherein n is 2 or more. n is, for example, 2 to 10, preferably 2 to 7, also preferably 2 to 6, and further preferably 2 to 3. R³The number of carbon atoms of (A) is, for example, 2 to 7, preferably 2 to 5. The larger the number of carbon atoms, the higher the hydrophobicity of the cured product, and the less likely the moisture will permeate through the cured product. The polyalkylene glycol di (meth) acrylate particularly preferably contains at least one compound selected from the group consisting of diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol dimethacrylate, tributylene glycol diacrylate (trimethylene glycol diacrylate), polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. The polyalkylene glycol di (meth) acrylate particularly preferably contains a compound selected from the group consisting of SR230, SR508NS, DPGDA, SR306NS, TPGDA, V310HP, APG200, SR205NS, LIGHT ACRYLATE PTMGA-250, SR231NS, LIGHT ESTER EG, SR205NS, LIGHT ESTER EG, SR210, SR NS, and SyntroAt least one compound selected from the group consisting of LIGHT ESTER 4EG manufactured by chemical industries, ACRYESTER HX manufactured by Mitsubishi chemical industries, and 3PG manufactured by Mitsubishi chemical industries.

The alkylene oxide-modified alkylene glycol di (meth) acrylate contains, for example, propylene oxide-modified neopentyl glycol. The alkylene oxide-modified alkylene glycol di (meth) acrylate may be, for example, EBECRYL145, product number manufactured by Daicel corporation.

When the acrylic compound (Y) contains the compound (Y11) having the structure represented by formula (200), the compound (Y11) preferably does not contain a compound having a value of n of 5 or more in formula (200). In (R)³In the case where-O) n is a polyethylene glycol skeleton, it is particularly preferable not to include a compound having a value of n of formula (200) of more than 5. Even in the case where the compound (Y11) contains a compound having a value of n of more than 5 in the formula (200), the percentage of the compound having a value of n of more than 5 in the formula (200) with respect to the acrylic compound (Y) is preferably 20% by mass or less. In addition, even when compound (Y11) contains a compound of formula (200) in which n has a value greater than 5, compound (Y11) preferably does not contain a compound of formula (200) in which n has a value greater than 9, and more preferably does not contain a compound of formula (200) in which n has a value greater than 7. In these cases, the viscosity of the composition (X) is particularly less likely to rise.

It is particularly preferable that the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di (meth) acrylate. The polyalkylene glycol di (meth) acrylate has a low viscosity and is less volatile, and therefore can contribute to a reduction in the viscosity of the composition (X), an improvement in the storage stability of the composition (X), and a reduction in the amount of outgas from the cured product.

When the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di (meth) acrylate, the proportion of polyalkylene glycol di (meth) acrylate to the acrylic compound (Y) is preferably 40% by mass or more and 80% by mass or less. When the proportion of the polyalkylene glycol di (meth) acrylate is 40% by mass or more, the viscosity of the composition (X) can be effectively reduced. When the proportion of the polyalkylene glycol di (meth) acrylate is 80% by mass or less, the proportion of the compound having three or more (meth) acryloyl groups in the molecule increases, and the reactivity of the composition (X) and the glass transition temperature of the cured product can be improved. The ratio is more preferably 42% by mass or more and 75% by mass or less, and still 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 a (meth) acryloyl group in one molecule. In this case, the polyfunctional acrylic compound (Y1) may contain, for example, at least one selected from 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 improved.

The polyfunctional acrylic compound (Y1) particularly 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. If the reactivity of the composition (X) is improved, the composition (X) can be easily cured even in an oxygen-containing environment such as an atmospheric atmosphere.

When the polyfunctional acrylic compound (Y1) contains pentaerythritol tetra (meth) acrylate, the proportion of pentaerythritol tetra (meth) acrylate to the acrylic compound (Y) is preferably 0.5% by mass or more and 10% by mass or less. In this case, the composition (X) can achieve both high reactivity and low viscosity. The ratio is more preferably 1% by mass or more and 9% by mass or less, and still 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. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, the shrinkage of the composition (X) during curing can be particularly reduced. In addition, the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide can be improved. The polyfunctional acrylic compound (Y1) particularly preferably contains at least one compound selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. These compounds are capable of reducing shrinkage particularly when the composition (X) is cured. These compounds also improve the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide.

When the cured product has improved adhesion to an inorganic material, high adhesion between the optical member and the inorganic material film is easily obtained when the optical member overlaps with a film made of an inorganic material such as a SiN film (inorganic film).

It is particularly preferable that 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 oxygen-containing environment such as an atmospheric atmosphere.

The acrylic compound (Y) preferably further contains a monofunctional acrylic compound (Y2) in which the radical polymerizable functional group in one molecule is only one (meth) acryloyl group. The monofunctional acrylic compound (Y2) can suppress shrinkage of the composition (X) during curing.

When the acrylic compound (Y) contains the monofunctional acrylic compound (Y2), the amount of the monofunctional acrylic compound (Y2) is preferably more than 0 mass% and 50 mass% or less with respect to the total amount of the acrylic compound (Y). If the amount of the monofunctional acrylic compound (Y2) is more than 0 mass%, shrinkage of the composition (X) upon curing can be suppressed. Further, if 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, and thus 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, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The monofunctional acrylic compound (Y2) may contain, for example, a compound selected from the group consisting of tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxyethyl acrylate, diethylene glycol monoethyl ether acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, omega-carboxy polycaprolactone monoacrylate, cyclohexyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, poly (meth) acrylic acid, poly (meth) acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3, 5-trimethylcyclohexyl 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, dicyclopentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, the ethylene oxide adduct of 2-phenoxyethyl acrylate, and mixtures thereof, At least one compound selected from the group consisting of 2-phenoxyethyl acrylate propylene oxide adducts, acryloylmorpholine, morpholin-4-yl acrylate, dicyclopentyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, 4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethyl cyclohexene oxide (3-methacryloyloxymethyl cyclohexene oxide) and 3-acryloyloxymethyl cyclohexene oxide (3-acryloxymethyl cyclohexene oxide).

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

Examples of the compound having an alicyclic structure include compounds selected from phenoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl ethoxylated acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloyl morpholine, morpholin-4-yl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1, 4-cyclohexanedimethanol monoacrylate.

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

The acrylic compound (Y) may contain a compound having silicon in a molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. The compound having silicon in the molecular skeleton contains, for example, at least one compound selected from 3- (trimethoxysilyl) propyl acrylate (e.g., product No. KBM5103 manufactured by shin-Etsu chemical industries, Ltd.) and an alkoxysilane oligomer having a (meth) acrylic group (e.g., product No. KR-513 manufactured by shin-Etsu chemical industries, Ltd.).

The acrylic compound (Y) may contain a compound having phosphorus in a molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. The compound having phosphorus in the molecular skeleton includes, for example, Acid phosphonoxy (meth) acrylate such as Acid phosphonoxypropyleneglycol monomethacrylate.

The acrylic compound (Y) may contain a compound having nitrogen in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Further, since the reactivity of the acrylic compound (Y) is easily improved, it is difficult to generate outgas from the cured product. The compound having nitrogen in the molecular skeleton contains, for example, at least one compound selected from the group consisting of compounds having a morpholine skeleton such as acryloylmorpholine, morpholin-4-yl acrylate, diethylacrylamide, dimethylaminopropylacrylamide, and pentamethylpiperidinyl methacrylate.

The acrylic compound (Y) particularly preferably 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 atmospheric atmosphere. The acrylic compound (Y) particularly preferably contains at least one of acryloyl morpholine and morpholin-4-yl acrylate. In this case, shrinkage of the composition (X) during curing can be suppressed. In addition, acryloyl morpholine and morpholin-4-yl acrylate have low viscosities, and therefore, these compounds do not readily increase the viscosity of composition (X). Further, these compounds are less likely to volatilize, and hence the storage stability of the composition (X) is easily improved.

The proportion 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 outgas is not easily generated from the cured product of the composition (X). The proportion is more preferably 7% by mass or more and 45% by mass or less, and still more preferably 10% by mass or more and 40% by mass or less.

The acrylic compound (Y) may contain a compound having an isobornyl skeleton. The compound having an isobornyl skeleton may contain, for example, one or more compounds selected from isobornyl acrylate and isobornyl methacrylate.

The acrylic compound (Y) may contain a component containing a compound having at least one skeleton selected from a dicyclopentadiene skeleton, a dicyclopentyl skeleton, a dicyclopentenyl skeleton, and a bisphenol skeleton. Specifically, the acrylic compound (Y) may contain at least one compound selected from tricyclodecane dimethanol diacrylate, bisphenol a polyethoxy diacrylate and bisphenol F polyethoxy diacrylate, for example. In this case, the adhesion between the cured product and the inorganic material can be improved.

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 improved, and the adhesion between the cured product and the inorganic material can be improved.

[ chemical formula 1 ]

In the formula (100), R⁰Is H or methyl. X is a single bond or a divalent hydrocarbon group. R¹～R¹¹Each is H, alkyl or-R¹²-OH，R¹²Is alkylene and R¹～R¹¹At least one of which is alkyl or-R¹²-OH。R¹～R¹¹Do not chemically bond to each other.

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

[ chemical formula 2 ]

The radically polymerizable compound (a1) may contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radical polymerizable compound (Z) is, for example, 10% by mass or less based on the total amount of the acrylic compound (Y) and the radical polymerizable compound (Z). The radically polymerizable compound (Z) may contain either or both of a polyfunctional radically polymerizable compound (Z1) having two or more radically polymerizable functional groups in one molecule and a monofunctional radically polymerizable compound (Z2) having only one radically polymerizable functional group in one molecule. The polyfunctional radical polymerizable compound (Z1) may contain, for example, at least one compound selected from the group consisting of an aromatic urethane oligomer having 2 or more ethylenic double bonds in one molecule, an aliphatic urethane oligomer, an epoxy acrylate oligomer, a polyester acrylate oligomer, and other special oligomers. The components that the polyfunctional radical polymerizable compound (Z1) may contain are not limited to the above components. The monofunctional radical polymerizable compound (Z2) contains, for example, at least one compound selected from the group consisting of N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1, 2-epoxybutane, 1, 3-butadiene monooxide, 1, 2-epoxydodecane, epichlorohydrin, 1, 2-epoxydecane, styrene oxide, epoxyhexane, 3-vinylepoxyhexane, 4-vinylepoxyhexane, N-vinylpyrrolidone and N-vinylcaprolactam. The components that the monofunctional radical polymerizable compound (Z2) may contain are not limited to the above components.

When the radical polymerizable compound (a1) contains the radical polymerizable compound (Z), the radical polymerizable compound (Z) may contain a compound having nitrogen in the molecular skeleton. The compound having nitrogen in the molecular skeleton contains, 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 the molecular skeleton, the adhesion between the cured product and the inorganic material is improved.

In other words, the radical polymerizable compound (a1) preferably contains a compound having nitrogen in the molecular skeleton. The compound having nitrogen in the molecular skeleton may contain a compound contained in the acrylic compound (Y) or a compound contained in the radical polymerizable compound (Z). In this case, the adhesion between the cured product and the inorganic material is improved. The proportion of the compound having nitrogen in the molecular skeleton to the entire radical polymerizable compound (a1) is preferably 5 mass% or more and 80 mass% or less. When the ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly easily improved. When the proportion is 80% by mass or less, the compound having nitrogen in the molecular skeleton does not easily inhibit the storage stability of the composition (X), and spatters are not easily generated when the composition (X) is ejected by an ink jet method (japanese: サテライト). Therefore, the ink-jettability of the composition (X) is not easily impaired. Further, it is possible to make it difficult to generate outgas due to a compound having nitrogen in the molecular skeleton. The proportion is more preferably 10% by mass or more and 70% by mass or less, still 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 ratio of the total amount of monofunctional compounds in the radically polymerizable compound (a1) (i.e., the total amount of the monofunctional acrylic compound (Y2) and the monofunctional radically polymerizable compound (Z2)) to the radically polymerizable compound (a1) is preferably 70% by mass or less. In this case, the generation of outgas due to the monofunctional compound is less likely to occur. The proportion is more preferably 60% by mass or less, and still more preferably 50% by mass or less.

The radical polymerizable compound (a1) particularly preferably contains at least one selected from acryloyl morpholine, morpholin-4-yl acrylate, diethylacrylamide and dimethylacrylamide. In this case, the absolute value of the difference between the first curing shrinkage and the second curing shrinkage is easily reduced. The total percentage of acryloyl morpholine, acrylic acid morpholin-4-yl ester, diethyl acrylamide and dimethyl acrylamide to the radical polymerizable compound (A) is preferably 15 mass% or more. In this case, the above-mentioned difference in cure shrinkage is particularly easily achieved. The percentage is more preferably 25 mass% or more, and still more preferably 35 mass% or more. The upper limit of the percentage is not particularly limited, and is, for example, 100 mass% or less. The percentage is preferably 85 mass% or less, and in this case, the hardness of the cured film can be easily adjusted to improve flexibility. The percentage is more preferably 70 mass% or less. In order to reduce the absolute value of the difference between the first curing shrinkage and the second curing shrinkage, it is preferable that the radically polymerizable compound (a1) does not contain isobornyl methacrylate, lauryl methacrylate, and 1, 6-hexanediol methacrylate.

The photo radical polymerization initiator (B1) is not particularly limited as long as it is a compound that generates radical species when irradiated with ultraviolet light. The photo radical polymerization initiator (B1) contains, for example, at least one compound selected from the group consisting of aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, sulfur compounds (e.g., thioxanthone compounds and thiophenyl group-containing compounds), hexaarylbiimidazole compounds, oxime ester compounds, borate ester compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds.

The photo radical polymerization initiator (B1) preferably further 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 photo radical polymerization initiator (B) preferably contains a component having at least one of a 9H-thioxanthen-9-one skeleton and an anthracene skeleton.

The photo radical polymerization initiator (B1) also preferably contains an oxime ester type photoinitiator. The oxime ester photoinitiator can improve curability of the composition (X). Therefore, even in an oxygen-containing atmosphere such as an atmospheric atmosphere, the composition (X) can be easily cured, and the outgas can be hardly generated from the cured product.

In order to prevent the composition (X) and the production apparatus from being contaminated by the decomposition product of the composition (X) and to prevent the emission of off-gas from the cured product, the oxime ester photoinitiator preferably contains a compound having an aromatic ring, more preferably a compound having a condensed ring containing an aromatic ring, and further preferably a compound having a condensed ring containing a benzene ring and a heterocycle.

The oxime ester photoinitiator may contain, for example, at least one compound selected from 1, 2-octanedione-1- [4- (phenylthio) -2- (benzoyloxime) ] and ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -, 1- (o-acetyloxime), and the oxime ester photoinitiators described in Japanese patent application laid-open Nos. 2000-80068, 2001-233842, 2010-527339, 2010-527338, 2013-041153 and 2015-93842. The oxime ester photoinitiator may contain at least one compound selected from commercially available Irgacure OXE-02 (manufactured by BASF) having a carbazole skeleton, ADEKA ARKLS NCI-831, N-1919 (manufactured by ADEKA) and TR-PBG-304 (manufactured by Changzhou super New electronic Material Co., Ltd.), Irgacure OXE-01 (manufactured by ADEKA) having a diphenyl sulfide skeleton, ADEKA ARKLS NCI-930 (manufactured by ADEKA), TR-PBG-345 and TR-PBG-3057 (manufactured by Changzhou super electronic Material Co., Ltd.), as well as TR-PBG-365 (manufactured by Changzhou super electronic Material Co., Ltd.) having a fluorene skeleton and SPI-04 (manufactured by Santana Ltd.). In particular, if the oxime ester photoinitiator contains a compound having a diphenylsulfide skeleton or a fluorene skeleton, the cured product is less likely to be colored by photobleaching, which is preferable. From the viewpoint of easy improvement in exposure sensitivity, it is preferable that the oxime ester photoinitiator contains a compound having a carbazole skeleton.

It is also preferable that the oxime ester photoinitiator contains two or more compounds. In this case, for example, when the oxime ester photoinitiator contains two or more compounds having different exposure sensitivities, the amount of the photo radical polymerization initiator (B) can be reduced while maintaining a good exposure sensitivity, and therefore, the outgas can be generated from the cured product more easily.

The proportion of the photo radical polymerization initiator (B1) to the radical polymerizable compound (a1) is preferably 6% by mass or more. In this case, the composition (X) can have good ultraviolet curability, and can also have good ultraviolet curability in an atmospheric atmosphere. The proportion is more preferably 7% by mass or more, and still 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 polymerization initiator (B) preferably contains a radical polymerization initiator (B3) having photobleachability. For example, the photo radical polymerization initiator (B1) preferably contains a photo radical polymerization initiator (B31) having photobleachability as the photopolymerization initiator (B3). When the composition (X) is irradiated with ultraviolet light, the photopolymerization initiator (B3) having photobleachability can improve the transparency of the composition (X) and a cured product thereof. Therefore, if the composition (X) is irradiated with ultraviolet rays, the ultraviolet rays easily reach the inside of the composition (X). Therefore, the composition (X) is easily and efficiently cured, and the difference between the first curing shrinkage and the second curing shrinkage is easily reduced.

The percentage of the photopolymerization initiator (B3) to the photopolymerization initiator (B) is preferably 50% by mass or more. In this case, the difference between the first cure shrinkage and the second cure shrinkage is particularly likely to be small. The percentage is more preferably 60 mass% or more, and still more preferably 75 mass% or more. The upper limit of the percentage is not particularly limited, and may be 100 mass%. That is, the percentage is, for example, 100 mass% or less.

When the photo radical polymerization initiator (B1) contains the photo radical polymerization initiator (B31), the photo radical polymerization initiator (B31) contains at least one of a compound having a photobleaching property in an oxime ester type photoinitiator and an acylphosphine oxide type photoinitiator, for example.

The oxime ester compound having a photobleachability contains at least one of a compound represented by the following formula (401) and a compound represented by the following formula (402), for example. Among them, the compound represented by the formula (402) has particularly high sensitivity, and therefore, particularly, it is easy to improve the photocurability of the composition (X), and therefore, it is easy to realize the ultraviolet curability of the composition (X) in the atmospheric atmosphere.

[ chemical formula 3 ]

[ chemical formula 4 ]

The acylphosphine oxide compound contains, for example, at least 1 selected from 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.

The radical polymerization initiator (B) preferably contains a photopolymerization initiator (B4) having an absorption coefficient of light having a wavelength of 405nm of 5ml/g cm or more. For example, the photo radical polymerization initiator (B1) preferably contains, as the photopolymerization initiator (B4), a photo radical polymerization initiator (B41) having an absorption coefficient of light having a wavelength of 405nm of 5ml/g · cm or more. When the composition (X) is irradiated with ultraviolet light, the photopolymerization initiator (B4) can improve the reactivity of the composition (X). Therefore, the difference between the first curing shrinkage and the second curing shrinkage is likely to be small.

The percentage of the photopolymerization initiator (B4) to the photopolymerization initiator (B) is preferably 50% by mass or more. In this case, the difference between the first cure shrinkage and the second cure shrinkage is particularly likely to be small. The percentage is more preferably 60 mass% or more, and still more preferably 75 mass% or more. The upper limit of the percentage is not particularly limited, and may be 100 mass%. That is, the percentage is, for example, 100 mass% or less.

When the photo radical polymerization initiator (B1) contains the photo radical polymerization initiator (B41), the photo radical polymerization initiator (B41) contains at least one selected from the group consisting of 2-benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (e.g., Irgacure369 manufactured by BASF), phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (e.g., Irgacure819 manufactured by BASF), 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide (e.g., Irgacure tpo manufactured by BASF), and bis (2, 4-cyclopentadienyl) bis [2, 6-difluoro-3- (1-pyrrolyl) phenyl ] titanium (IV) (e.g., Irgacure784 manufactured by BASF), for example.

The compound contained in the photopolymerization initiator (B3) and the compound contained in the photo radical polymerization initiator (B4) may be repeated. That is, in the case where the composition (X) contains the photopolymerization initiator (B3), the photopolymerization initiator (B3) may contain at least a part of the photo radical polymerization initiator (B4). In addition, in the case where the composition (X) contains the photopolymerization initiator (B4), the photopolymerization initiator (B4) may contain at least a part of the photo radical polymerization initiator (B3).

The composition (X) may further contain a polymerization accelerator in addition to the photo radical polymerization initiator (B1). The polymerization accelerator includes, for example, amine compounds such as ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxyethyl p-dimethylaminobenzoate, and the like. The components that the polymerization accelerator may contain are not limited to the above components.

When the photopolymerizable compound (a) contains the cationically polymerizable compound (a2), the cationically polymerizable compound (a2) contains at least one of the polyfunctional cationically polymerizable compound (W1) and the monofunctional cationically polymerizable compound (W2), for example.

The polyfunctional cationic polymerizable compound (W1) may contain either one or both of the polyfunctional cationic polymerizable compound (W11) having no siloxane skeleton and the polyfunctional cationic polymerizable compound (W12) having a siloxane skeleton.

The polyfunctional cationically polymerizable compound (W11) has no siloxane skeleton and two or more cationically polymerizable functional groups in one molecule. The number of the cationic polymerizable functional groups per molecule of the polyfunctional cationic polymerizable compound (W11) is preferably 2 to 4, and more preferably 2 to 3.

The cationically polymerizable functional group is, for example, at least one group selected from an epoxy group, an oxetanyl group and a vinyl ether group.

The polyfunctional cationic polymerizable compound (W11) contains, for example, at least one compound selected from the group consisting of a polyfunctional alicyclic epoxy compound, a polyfunctional heterocyclic epoxy compound, a polyfunctional oxetane compound, an alkylene glycol diglycidyl ether, and an alkylene glycol monovinyl monoglycidyl ether.

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

[ chemical formula 5 ]

In the formula (1), R¹～R¹⁸Each independently a hydrogen atom, a halogen atom or a hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20. The hydrocarbon group is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, etc.; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an alkylidene group having 2 to 20 carbon atoms such as ethylidene group or propylidene group. The hydrocarbon group may contain an oxygen atom or a halogen atom. R¹～R¹⁸Each independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

In the formula (1), X is a single bond or a divalent organic group such as-CO-O-CH₂-。

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

[ chemical formula 6 ]

[ chemical formula 7 ]

[ chemical formula 8 ]

In the formula (20), R¹～R¹²Each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The hydrocarbon group having 1 to 20 carbon atoms is, for example, methyl group or ethyl groupAlkyl groups having 1 to 20 carbon atoms such as a mesityl group and propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group or an allyl group; or an alkylidene group having 2 to 20 carbon atoms such as ethylidene group or propylidene group. The hydrocarbon group having 1 to 20 carbon atoms may contain an oxygen atom or a halogen atom.

R¹～R¹²Each independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

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

[ chemical formula 9 ]

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

[ chemical formula 10 ]

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

[ chemical formula 11 ]

The alkylene glycol diglycidyl ether contains, for example, at least one compound selected from the compounds represented by the following formulae (4) to (7).

[ chemical formula 12 ]

[ chemical formula 13 ]

[ chemical formula 14 ]

[ chemical formula 15 ]

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

[ chemical formula 16 ]

More specifically, the polyfunctional cation polymerizable compound (W11) may contain at least one component selected from the group consisting of CELLOXIDE2021P and CELLOXIDE 8010 manufactured by Daicel, TEPIC-VL manufactured by Nissan Chemicals, OXT-221 manufactured by Toyo chemical Co., Ltd, and 1, 3-PD-DEP manufactured by Siri City, 1, 4-BG-DEP, 1, 6-HD-DEP, NPG-DEP, and butanediol monovinyl monoglycidyl ether.

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

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

When the polyfunctional alicyclic epoxy compound contains a compound represented by the formula (1), the compound represented by the formula (1) preferably contains a compound represented by the formula (1 a). 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, and therefore, when the compound represented by formula (20) is contained, the composition (X) can have a particularly low viscosity as well as good ultraviolet curability. Further, the compound represented by the formula (20) has a property of being less volatile even if it has a low viscosity. Therefore, even if the composition (X) contains the compound represented by the formula (20), the composition (X) is less likely to undergo a change in composition due to volatilization of the compound represented by the formula (20). Therefore, the composition (X) can be made low in viscosity without impairing storage stability by containing the compound represented by formula (20).

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

The compound represented by formula (20) may contain 4 stereoisomers based on the stereoconfiguration of 2 epoxy rings. The compound represented by formula (20) may contain any one of 4 stereoisomers. That is, the compound represented by formula (20) may contain at least one component selected from 4 stereoisomers. The total amount of exo-endo forms and endo forms in the 4 stereoisomers in the compound represented by formula (20) is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total epoxy compound (a 1). In this case, the heat resistance of the cured product can be improved. The ratio of the 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 amount of exo-endo forms and endo-endo forms in the compound represented by formula (20), an appropriate method such as a method of subjecting the compound represented by formula (20) to precise distillation, a method of using column chromatography using silica gel or the like as a filler, or the like can be used.

When the composition (X) contains the polyfunctional cationically polymerizable compound (W11), the ratio of the polyfunctional cationically polymerizable compound (W11) to the total amount of the resin components is preferably 5% by mass or more and 95% by mass or less. The resin component is a compound having cationic polymerizability in the composition (X), and includes a polyfunctional cationic polymerizable compound (W1) and a monofunctional cationic polymerizable compound (W2). When the proportion of the polyfunctional cationically polymerizable compound (W11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity in the photo cationic polymerization reaction, and the cured product can have high strength (hardness). Further, if the proportion of the polyfunctional cation polymerizable compound (W11) is 95% by mass or less, when the composition (X) contains the moisture absorbent (E), the moisture absorbent (E) can be easily dispersed particularly uniformly in the composition (X). The proportion of the polyfunctional cation polymerizable compound (W11) is more preferably 12% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The proportion of the polyfunctional cation polymerizable compound (W11) is more preferably 85 mass% or less, and still more preferably 60 mass% or less. For example, the proportion of the polyfunctional cation polymerizable compound (W11) is preferably 20 mass% or more and 60 mass% or less.

When the polyfunctional cationically polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of or the whole polyfunctional cationically polymerizable compound (W11). The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (W11) is preferably in the range of 15 to 100% by mass. When the content is 15% by mass or more, the polyfunctional alicyclic epoxy compound can contribute particularly to improvement of ultraviolet curability 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 the cationic polymerizable functional groups per molecule of the polyfunctional cationic polymerizable compound (W12) is preferably 2 to 6, and more preferably 2 to 4. The polyfunctional cationically polymerizable compound (W12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X) and can contribute to the improvement of the heat discoloration resistance of the cured product and the optical member. The polyfunctional cationically polymerizable compound (W12) can also contribute to a low elastic modulus of a cured product and an optical member. When the composition (X) contains a moisture absorbent, the polyfunctional cation polymerizable compound (W12) can also contribute to improvement in dispersibility of the moisture absorbent in the composition (X) and in the cured product.

The polyfunctional cationically polymerizable compound (W12) is preferably liquid at 25 ℃. In particular, the viscosity of the polyfunctional cationically polymerizable compound (W12) is preferably in the range of 10 to 300 mPas at 25 ℃. In this case, the viscosity of the composition (X) can be inhibited from increasing.

The cationic polymerizable functional group of the polyfunctional cationic polymerizable compound (W12) is, for example, at least one group selected from an epoxy group, an oxetanyl group and a vinyl ether group.

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

[ chemical formula 17 ]

[ chemical formula 18 ]

R in each of the formulae (10) and (11) is a single bond or a divalent organic group, and is preferably an alkylene group. Y is a siloxane skeleton, and may be any of linear, branched and cyclic, and the number of Si atoms is preferably in the range of 2 to 14, more preferably in the range of 2 to 10, further 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 to 4.

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

[ chemical formula 19 ]

R in the formula (10a) is a single bond or a divalent organic group, and is preferably an alkylene group having 1 to 4 carbon atoms. N in the 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, further preferably in the range of 0 to 5, and particularly preferably in the range of 1 to 4.

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

More specifically, the polyfunctional cationic polymerizable compound (W12) preferably contains at least one component selected from the group consisting of trade names X-40-2669, X-40-2670, X-40-2715, X-40-2732, X-22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163 and X-22-163B available from shin-Etsu chemical Co., Ltd.

The polyfunctional cationically polymerizable compound (W12) preferably has an alicyclic epoxy structure, and the polyfunctional cationically polymerizable compound (W12) particularly preferably contains a compound represented by the formula (10 a). The compound represented by the formula (10a) can contribute particularly to the improvement of the cationic polymerization reactivity and the reduction of the viscosity of the composition (X), and can contribute particularly to the improvement of the heat discoloration resistance and the reduction of the elastic modulus of a cured product and an optical member. When the composition (X) contains the moisture absorbent (E), the dispersibility of the moisture absorbent (E) in the composition (X) can be particularly improved.

When the composition (X) contains the polyfunctional cationically polymerizable compound (W12), the ratio of the polyfunctional cationically polymerizable compound (W12) to the total amount of the resin components is preferably in the range of 5 to 95% by mass. In this case, particularly, if 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 particularly high photo cation polymerization reactivity.

The monofunctional cationically polymerizable compound (W2) has only one cationically polymerizable functional group per molecule. The cationically polymerizable functional group is, for example, at least one group selected from an epoxy group, an oxetanyl group and a vinyl ether group.

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

The monofunctional cation polymerizable compound (W2) may contain at least one compound selected from the compounds represented by the following formulae (12) to (17) and limonene oxide, for example.

[ chemical formula 20 ]

[ chemical formula 21 ]

[ chemical formula 22 ]

[ chemical formula 23 ]

[ chemical formula 24 ]

[ chemical formula 25 ]

The proportion of the monofunctional cationically polymerizable compound (W2) to the total amount of the resin component is preferably in the range of 5 to 50% by mass. When the proportion of the monofunctional cationically polymerizable compound (W2) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. Further, if the proportion of the monofunctional cationically polymerizable compound (W2) is 50% by mass or less, the composition (X) can have particularly excellent reactivity in the photo-cationic polymerization reaction, and thus can impart high strength (hardness) to a cured product. The proportion of the monofunctional cationically polymerizable compound (W2) is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The proportion of the monofunctional cation polymerizable compound (W2) is more preferably 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably 30% by mass or less. In particular, if the proportion of the monofunctional cation polymerizable compound (W2) is 35% by mass or less, the volatilization amount of components in the composition (X) during storage of the composition (X) can be effectively reduced, and therefore, even if the composition (X) is stored for a long time, the properties of the composition (X) are not easily impaired. In addition, the occurrence of tackiness in the cured product can be particularly suppressed. For example, the proportion of the monofunctional cationically polymerizable compound (W2) is preferably within a range of 10 to 35% by mass.

In particular, when the composition (X) contains the polyfunctional cationic polymerizable compound (W11) and the polyfunctional cationic polymerizable compound (W12), the ratio of the polyfunctional cationic polymerizable compound (W11) is preferably in the range of 30 to 60 mass%, the ratio of the polyfunctional cationic polymerizable compound (W12) is in the range of 15 to 30 mass%, and the ratio of the monofunctional cationic polymerizable compound (W2) is preferably in the range of 15 to 40 mass%, based on the total amount of the resin components. In this case, the composition (X) can achieve good storage stability, low viscosity, and good cationic polymerization reactivity in a well-balanced manner, and can achieve excellent transparency, excellent moisture absorption, and a high refractive index of the cured product in a well-balanced manner.

When the cationically polymerizable compound (a2) contains the compound represented by formula (3) and the compound represented by formula (16), the ease of progress of the curing reaction in the production of a photo-cured product from the composition (X) can be adjusted to an appropriate level by adjusting the ratio of the two compounds, and the composition (X) can be made to have a low viscosity and improved storage stability.

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

The cation polymerizable compound (a2) preferably contains a compound (f1) (hereinafter, also referred to as an aromatic epoxy compound (f1)) represented by the following formula (30).

[ chemical formula 26 ]

In the 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 a plurality of X are present in one molecule, they may be the same or different from each other. Hydrocarbyl is for example alkyl or aryl. When X is a hydrocarbon group, the number of carbon atoms of X is, for example, in the range of 1 to 10. R is a single bond or a divalent organic group. In the case where R is a divalent organic group, the divalent organic group is, for example, alkylene, oxyalkylene, carbonyloxyalkylene (e.g., -CO-O-CH)₂-, or-C (Ph)₂-O-CH₂-a radical. Y is H or a monovalent organic group. In the case where 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, and therefore the aromatic epoxy compound (f1) tends to lower the viscosity of the composition (X). Further, since the aromatic epoxy compound (f1) is less likely to volatilize, 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 (f 1). 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, unreacted components are less likely to remain in the cured product, and outgassing from the cured product is less likely to occur. In addition, the aromatic epoxy compound (f1) easily increases the glass transition temperature of the cured product, and thus easily improves the heat resistance of the cured product.

In addition, in the case where the composition (X) is discharged by the ink jet method, the aromatic epoxy compound (f1) is less likely to generate defective droplets called splash.

R in formula (30) is preferably a single bond or an alkylene group. In the case where n in formula (30) is 2 or 3, it is preferable that at least one of the plurality of R in formula (30) is a single bond or an alkylene group. In these cases, the reactivity of the aromatic epoxy compound (f1) tends to be high, and thus the curability of the composition (X) when the composition (X) is irradiated with ultraviolet light tends to be high.

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

[ chemical formula 27 ]

Particularly preferably, the aromatic epoxy compound (f1) contains at least one component selected from the group consisting of the compounds represented by the formulae (301) to (305), (312), (314) and (318). These compounds are likely to have high reactivity because at least one epoxy group (ethylene oxide) in the compound is bonded to a benzene ring by a single bond or an alkylene group, and thus the curability of the composition (X) is likely to be improved.

The proportion of the aromatic epoxy compound (f1) to the entire cationically polymerizable compound (a2) is preferably 5% by mass or more. In this case, the above-mentioned effect of the aromatic epoxy compound (f1) is particularly easily obtained. The proportion is also preferably 95% by mass or less. In this case, the composition (X) can be easily stored well. The proportion is more preferably 10% by mass or more and 90% by mass or less, and still more preferably 20% by mass or more and 85% by mass or less.

It is also preferable that the cationically polymerizable compound (a2) contains a compound (f2) having an oxyalkylene skeleton. The oxyalkylene skeleton means a linear skeleton containing one or more linear oxyalkylene units.

If the cationically polymerizable compound (a2) contains the compound (f2), the compound (f2) has a low viscosity, and therefore the compound (f2) tends to lower the viscosity of the composition (X). Further, since the compound (f2) is less likely to volatilize, 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 (f 1). Therefore, the compound (f2) can easily improve the storage stability of the composition (X).

In addition, the compound (f2) makes it less likely to generate defective droplets called splash when the composition (X) is ejected by an ink jet method. Further, even if the velocity of the liquid droplet ejected by the ink jet method is increased, the compound (f2) can make the splash less likely to occur. Therefore, although it depends on the conditions of ink ejection, for example, the ejection speed of droplets by the ink jet method can be set to 4m/s or more without generating spatters. If the velocity of the droplets can be increased, the trajectory of the droplets is less susceptible to external disturbances, and therefore the dimensional accuracy of the cured product produced from the composition (X) can be improved. Further, as described above, since the compound (f2) can improve the storage stability of the composition (X), the composition (X) can be stored for a long period of time, and thus the characteristics of the composition (X) that are less likely to generate spatters can be easily maintained.

The oxyalkylene skeleton particularly preferably comprises the structure "-C-O-", i.e.oxymethylene units. In this case, the splash is particularly less likely to occur, and for example, the splash is less likely to occur even if the driving frequency at which the composition (X) is discharged by the ink jet method is changed. Further, the compound (f2) is less volatile and can easily attain a lower viscosity, and the affinity (wettability) of the composition (X) for inorganic materials can be easily improved.

The number of oxyalkylene units in the oxyalkylene skeleton in the compound (f2) is preferably 1 or more and 8 or less. In this case, the compound (f2) tends to have a lower viscosity, and therefore, spatter is particularly unlikely to occur, and the crosslink density of the cured product tends to be high, and therefore, the glass transition temperature of the cured product tends to be particularly high. The number of oxyalkylene units is more preferably 1 or more and 6 or less, and still more preferably 1 or more and 4 or less.

In the compound (f2), a substituent other than hydrogen may be bonded to the oxyalkylene unit in the oxyalkylene skeleton. For example, the oxymethylene unit contained in the oxyalkylene skeleton may have "-CH (CH)₃)-CH₂-O- "structure.

The proportion of the compound (f2) is preferably 10% by mass or more relative to the cationically polymerizable compound (a 2). In this case, the ink ejection property is good, and the wettability to the substrate is good. The proportion is preferably 70% by weight or less. In this case, the glass transition temperature can be sufficiently increased. The proportion is more preferably 15% by mass or more and 60% by mass or less, and still more preferably 20% by mass or more and 50% by mass or less.

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

The compound (f21) contains, for example, at least one compound selected from the group consisting of 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 (8), the compound represented by the formula (13), the compound represented by the formula (14), and the like. The component that compound (f21) may contain is not limited to the above-mentioned components.

The compound (f22) contains, for example, at least one compound selected from the group consisting of 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). The component that compound (f22) may contain is not limited to the above-mentioned components.

The cationically polymerizable compound (a2) preferably further contains an epoxy compound and the above-mentioned compound (f 22). The epoxy compound contains, for example, at least one compound having an epoxy group among the compounds that can be contained in the cationically polymerizable compound (a 2). When the cationically polymerizable compound (a2) contains an epoxy compound and a compound (f22), the curability of the composition (X) when the composition (X) is irradiated with ultraviolet light is likely to be improved, and the composition (X) is less likely to cause excessively severe curing, so that the cured product is less likely to be deteriorated in transparency due to cloudiness or the like. The mechanism for producing this effect is presumed as follows. Since the reactivity of the compound (f22) is lower than that of the epoxy compound, if the composition (X) is irradiated with ultraviolet light, the epoxy compound reacts first. The epoxy compound is reacted, whereby the curability of the composition (X) is easily increased. Next, the compound (f22) reacts, whereby the epoxy compound and the compound (f22) do not easily react with each other. This is considered to be unlikely to cause an excessively violent reaction. The proportion of the compound (f22) in this case to the cationically polymerizable compound (a2) is preferably 20% by mass or more. In this case, the compound (f22) makes it particularly easy to reduce the viscosity of the composition (X) and particularly improves the storage stability of the composition (X). Further, the compound (f22) can particularly easily improve the curability of the composition (X). The proportion of the compound (f22) is also preferably 90% by mass or less. In this case, the curability of the cured product can be sufficiently improved. The proportion of the compound (f22) is more preferably 10% by mass or more and 90% by mass or less, and still more preferably 20% by mass or more and 80% by mass or less. The proportion of the epoxy compound in this case is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and still more preferably 25% by mass or more and 75% by mass or less, relative to the total amount of the cationically polymerizable compound (a 2). In these cases, the unreacted groups in the cured product can be sufficiently reduced, and the curability of the cured product can be sufficiently improved.

The epoxy compound preferably contains a compound having at least one oxirane ring which does not constitute a glycidyl ether group. In this case, the epoxy compound is particularly likely to improve the curability of the composition (X). It is more preferable if the epoxy compound contains a compound having two or more oxirane rings which do not constitute a glycidyl ether group. The epoxy compound also preferably contains a compound having no glycidyl ether group. It is particularly preferable if the epoxy compound contains a compound having two or more oxirane rings not constituting a glycidyl ether group and having no glycidyl ether group.

It is particularly preferable that the cationically polymerizable compound (a2) contains the compound (f2) and an epoxy compound, and the epoxy compound contains the aromatic epoxy compound (f 1). In this case, the composition (X) tends to have particularly excellent storage stability, and when the composition (X) is ejected by an ink jet method, defective droplets called splash are particularly unlikely to be generated. In addition, even if the velocity of the liquid droplets discharged by the ink jet method is increased, the splash can be prevented from being generated. Further, even when the composition (X) is stored for a long period of time, the composition (X) is particularly easy to maintain the characteristics of the composition (X) that are less likely to generate spatters. In this case, it is particularly preferable that the compound (f2) contains the compound (f 22).

The ratio of the total of the aromatic epoxy compound (f1) and the compound (f22) to the cationically polymerizable compound (a2) is preferably 55% by mass or more. In this case, the effect of the combination of the aromatic epoxy compound (f1) and the compound (f22) is particularly remarkable. The proportion is more preferably 60% by mass or more, and still more preferably 70% by mass or more. Particularly preferably, the cationically polymerizable compound (a2) contains only the aromatic epoxy compound (f1) and the compound (f 22).

From the viewpoint of reactivity, the cationically polymerizable compound (a2) is preferably an alicyclic epoxy. Specifically, the cationically polymerizable compound (A2) contains, for example, at least one compound selected from the group consisting of a compound represented by the formula (20a) (e.g., THI-DE, product number manufactured by JX energy Co., Ltd.), a compound represented by the formula (1a) (e.g., CELLOXIDE 8010, product number manufactured by Daicel Co., Ltd.), a compound represented by the formula (1b) (e.g., CELLOXIDE2021P, product number manufactured by Daicel Co., Ltd.), and a limonene dioxide (e.g., LDO, product number manufactured by Arkema Co., Ltd.). The percentage of the cationically polymerizable compound (a2) to the whole cationically polymerizable compound (a) is preferably 40% by mass or more.

The photo cation polymerization initiator (B2) is not particularly limited as long as it is a catalyst that generates a protonic acid or a lewis acid by irradiation with light. The photo-cationic polymerization initiator (B2) may contain at least one of an ionic photo-acid type cationic curing catalyst and a nonionic photo-acid type cationic curing catalyst.

The ionic photoacid-type cationic curing catalyst may contain at least one of an onium salt and an organic metal complex. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of the organic metal complex include iron-arene complexes, titanocene complexes, and aryl silanol-aluminum complexes. The cationic curing catalyst of the ionic photoacid type may contain at least one of these components.

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

More specific examples of the compound that the photocationic polymerization initiator (B2) may contain include: the 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, 1003, 100, etc.), TSP series (103, 105, 100, 1000, etc.), etc., 100, etc.), TSP series, 100, etc., TSP series, 100, etc., MDS series, etc., NDS series, 103, 105, 109, 165, 109, etc., NDS, etc., and the like manufactured by Midori series, HDS series, 109, HDS series, HDS-109, HDS, and the like, 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 Bisphingol 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 of America;

irgacure 250, Irgacure 261 and Irgacure 264 from BASF corporation;

CG-24-61 manufactured by CIBA-GEIGYAG;

ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-151, ADEKA OPTOMER SP-170 and ADEKA OPTOMER SP-171, manufactured by ADEKA, Inc.;

DAICAT II manufactured by Daicel, Inc.;

UVAC 1590 and UVAC 1591 manufactured by Daicel Cytech;

CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 and CIT-1682, all of which are manufactured by Nippon Caoda corporation;

toluoyl cumyl iodonium tetrakis (pentafluorophenyl) borate PI-2074 manufactured by 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 manufactured by San-Apro; and

UVI-6992 and UVI-6976 manufactured by Dow Chemical Co. The photo cation polymerization initiator (B2) may contain at least one compound selected from these compounds.

The ratio of the photo-cationic polymerization initiator (B2) to the cationically polymerizable compound (A2) is preferably in the range of 1 to 4% by mass. When the proportion is 1% by mass or more, the composition (X) can have particularly good cationic polymerization reactivity. In addition, by setting the ratio to 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 amount of the photo cation polymerization initiator (B2).

The composition (X) may contain a sensitizer (C). In this case, the sensitizer (C) can promote the reaction of the photopolymerization initiator (B), and thus the difference between the first curing shrinkage and the second curing shrinkage of the composition (X) can be easily reduced.

The sensitizer (C) may contain, for example, at least one compound selected from the group consisting of 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, anthraquinone, 1, 2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1, 4-diethoxynaphthalene, p-dimethylaminoacetophenone, p-diethylaminoacetophenone, p-dimethylaminobenzophenone, p-diethylaminobenzophenone, 4 '-bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, p-dimethylaminobenzaldehyde and p-diethylaminobenzaldehyde. The sensitizer (C) may contain any component, but is not limited to the above-described components.

The sensitizer (C) preferably contains at least one of an anthracene compound and an anthraquinone compound. The anthracene compound contains at least one selected from 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, 9-hydroxymethylanthracene, and the like, for example. The thioxanthone-based compound contains at least one selected from the group consisting of thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, and the like, for example.

The sensitizer (C) particularly preferably contains an anthracene compound. In this case, since the transparency of the composition (X) is not easily impaired, the coating film of the composition (X) is easily cured uniformly from the surface layer to the deep part, and thus the cured product is particularly less likely to have irregularities.

The percentage of the sensitizer (C) with respect to the composition (X) is preferably 0.05% by mass or more. In this case, the reactivity of the composition (X) is particularly likely to be high, and thus the difference between the first cure shrinkage and the second cure shrinkage is particularly likely to be small. The percentage is more preferably 0.1 mass% or more, and still more preferably 0.3 mass% or more. The percentage of the sensitizer (C) is preferably 2.0 mass% or less. In this case, the coating film of the composition (X) is easily cured uniformly from the surface layer to the deep part, and thus the cured product is particularly less likely to have unevenness. The percentage is more preferably 1.5 mass% or less, and still more preferably 1.0 mass% or less.

The composition (X) may contain a leveling agent (D). The leveling agent (D) easily smoothes the surface of the coating film of the composition (X). Therefore, when the coating film is irradiated with ultraviolet rays, the coating film is easily cured uniformly, and thus the cured product is particularly less likely to have irregularities.

The leveling agent (D) preferably contains a silane compound (D1). The silane compound (D1) preferably contains a silane compound (D11) having a nitrogen atom and an alkoxysilyl group. In this case, since the composition (X) and the cured product have improved affinity for inorganic materials such as silicon nitride, the smoothness of the coating film and the cured film is particularly likely to be improved. The silane compound (D11) particularly preferably contains a silane compound (D12) having an azacyclopentane skeleton (pyrrolidine skeleton). In this case, the smoothness of the coating film and the cured film is particularly easily improved. The silane compound (D12) has a structure in which, for example, an alkoxy group is bonded to Si in the azacyclopentane skeleton, and an organic group such as a hydrocarbon group is bonded to nitrogen in the azacyclopentane skeleton. Hydrocarbyl is for example aryl, alkyl, alkenyl or alkynyl.

The silane compound (D12) preferably contains an azasilacyclopentane-type silane. The azasilacyclopentane-type silane has, for example, a structure represented by the following formula (4).

[ chemical formula 28 ]

In the formula (4), R¹And R²Are each an alkyl group. X is an organic group, for example a hydrocarbon group.

R¹And R²The number of carbon atoms of each is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2.

In the case where X is a hydrocarbon group, the hydrocarbon group is, for example, an aryl group, an alkyl group, an alkenyl group or an alkynyl group. The number of carbon atoms of the hydrocarbon group is preferably 3 or more and 20 or less, more preferably 4 or more and 17 or less, and further preferably 6 or more and 14 or less. Specifically, examples of the hydrocarbon group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, octyl group, and tetradecyl group; branched alkyl groups such as isopropyl, tert-butyl and isobutyl; cyclic alkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as phenethyl and diphenylmethyl.

The silane compound (D11) contains at least one selected from the group consisting of 2, 2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane, 2-dimethoxy-1-octyl-1-aza-2-silacyclopentane, 2-dimethoxy-1-tetradecyl-1-aza-2-silacyclopentane, and the like, for example.

The compound that the silane compound (D1) may contain is not limited to the above silane compound (D11). The silane compound (D1) may contain a suitable organoalkoxysilane, for example, the silane compound (D1) may contain at least one compound selected from N-phenyl-3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, hexyltrimethoxysilane and the like.

In addition, the compound that the leveling agent (D) may contain is not limited to the silane compound (D1). For example, the leveling agent (D) may contain at least one compound selected from the group consisting of a fluorine compound, an acrylic copolymer and an alcohol alkoxylate compound.

The percentage of the leveling agent (D) with respect to the composition (X) is preferably 0.1 mass% or more. In this case, the cured product is less likely to have unevenness. The percentage is more preferably 0.3 mass% or more, and still more preferably 0.5 mass% or more. The percentage of the leveling agent (D) is preferably 3.0 mass% or less. In this case, there is an advantage that it is possible to prevent the ink ejection property from being deteriorated due to an excessive decrease in the surface tension. The percentage is more preferably 2.5 mass% or less, and still more preferably 2.0 mass% or less.

The composition (X) may further contain a moisture absorbent (E). If the composition (X) contains the moisture absorbent (E), the cured product of the composition (X) and the sealing material 5 can have moisture absorption properties. Therefore, the sealing material 5 can make the light-emitting element 4 in the light-emitting device 1 less likely to be penetrated by moisture. The average particle diameter of the moisture absorbent (E) is preferably 200nm or less. In this case, the cured product can have high transparency.

The moisture absorbent (E) is preferably an inorganic particle having moisture absorption properties, and preferably contains at least one component selected from zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles, for example. Particularly preferably, the moisture absorbent (E) contains zeolite particles.

The zeolite particles having an average particle diameter of 200nm or less can be produced by, for example, pulverizing a conventional industrial zeolite. In the production of zeolite particles, zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like, and in this case, the zeolite particles can have particularly high hygroscopicity. Examples of such a method for producing zeolite particles are disclosed in japanese patent application laid-open nos. 2016 and 69266 and 2013 and 049602.

When the composition (X) contains the moisture absorbent (E), the proportion of the moisture absorbent (E) to the total amount of the composition (X) is preferably 1 mass% or more and 20 mass% or less. When the proportion of the moisture absorbent (E) is 1% by mass or more, the cured product can have particularly high moisture absorption. In addition, if the proportion 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) can have a sufficiently low viscosity to the extent that it can be applied by an ink jet method. The proportion of the moisture absorbent (E) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The proportion 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). In particular, the composition (X) preferably contains nano-sized high refractive index particles. Examples of the high refractive index particles include zirconia particles. When the composition (X) contains high-refractive-index particles, the refractive index of the cured product can be increased while maintaining good transparency of the cured product. Therefore, when the cured product is applied to the sealing material 5 in the light-emitting device 1, the efficiency of extracting light emitted to the outside through the sealing material 5 can be improved. The average particle diameter of the high refractive index particles is preferably within a range of 5 to 30nm, and more preferably within a range of 10 to 20 nm.

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

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

The structure of the light-emitting device 1 will be explained. The light-emitting device 1 includes a light source and an optical member that transmits light emitted from the light source. For example, the light-emitting device 1 includes a light-emitting element 4, a sealing material 5 covering the light-emitting element 4, and a passivation layer 6. In this case, the light emitting element 4 is a light source, the sealing material 5 is an optical member, and the passivation layer 6 is an inorganic layer. The sealing material 5 overlaps the passivation layer 6.

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

An example of the structure of the light-emitting device 1 is described with reference to fig. 1. The 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 located on a surface of the support substrate 2 facing the transparent substrate 3, and a passivation layer 6 and a sealing material 5 covering the light-emitting element 4.

The support substrate 2 is made of, for example, a resin material, but is not limited thereto. The transparent substrate 3 is made of a material having translucency. 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 located 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 stacked in this order.

The light-emitting device 1 includes a plurality of light-emitting elements 4, and the plurality of light-emitting elements 4 form an array 9 (hereinafter referred to as an element array 9) on the support substrate 2. The element array 9 further includes a partition wall 7. The partition wall 7 is located on the support substrate 2 and partitions between the adjacent two light emitting elements 4. The partition wall 7 is formed by, for example, molding a photosensitive resin material by photolithography. The element array 9 further includes a connection wiring 8 for electrically connecting the electrode 43 of the adjacent light-emitting element 4 and the electron transit layer 424 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, and particularly preferably made of silicon nitride. In the example shown in fig. 1, the passivation layer 6 comprises a first passivation layer 61 and a second passivation layer 62. The first passivation layer 61 covers the element array 9 in a state of being in direct contact with the element array 9, thereby covering the light emitting elements 4. The second passivation layer 62 is disposed at a position opposite to the element array 9 with respect to the first passivation layer 61, and is spaced apart from the first passivation layer 61 by a space between the second passivation layer 62. The sealing material 5 is filled between the first passivation layer 61 and the second passivation layer 62. That is, the first passivation layer 61 is interposed between the light emitting element 4 and the sealing material 5 covering the light emitting element 4.

Further, the second sealing material 52 is filled between the second passivation layer 62 and the transparent substrate 3. The second sealing member 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 using the composition (X) and a method for producing the light-emitting device 1 will be described.

In the present embodiment, it is preferable that the sealing material 5 is prepared by molding the composition (X) by an ink jet method and then curing the composition (X) by irradiating the composition with ultraviolet rays. In the present embodiment, the composition (X) can be formed by applying the composition by an ink jet method.

When the composition (X) is applied by the ink jet method, the composition (X) can be formed by applying the composition (X) by the ink jet method without heating when the composition (X) has a sufficiently low viscosity at room temperature, for example, a viscosity of 30mPa · s or less, particularly 15mPa · s or less at 25 ℃.

When the composition (X) has a property of being reduced in viscosity by heating, the composition (X) may be heated and then applied by an ink jet method to be molded. When the viscosity of the composition (X) at 40 ℃ is 30 mPas or less, particularly 15 mPas or less, the viscosity can be reduced by heating the composition (X) only a little, and the composition (X) having a reduced viscosity can be discharged by an ink jet method. The heating temperature of the composition (X) is, for example, 20 ℃ or more and 50 ℃ or less.

More specifically, for example, the support substrate 2 is first prepared. The partition walls 7 are formed on one surface of the support substrate 2 by photolithography using, for example, a photosensitive resin material. Next, a plurality of light emitting elements 4 are provided on one surface of the support substrate 2. The light-emitting element 4 can be manufactured by an appropriate method such as a vapor deposition method or a coating method. In particular, the light-emitting element 4 is preferably manufactured by an application method such as an ink-jet method. Thereby, the element array 9 is produced on the support substrate 2.

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

Next, the composition (X) is formed on the first passivation layer 61 by, for example, an ink-jet method, thereby producing a coating film. If the ink jet 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. Next, the coating film of the composition (X) is irradiated with ultraviolet rays and cured to produce the sealing material 5. The thickness of the sealing material 5 is, for example, 5 μm or more and 50 μm or less.

When the composition (X) is irradiated with ultraviolet light, the composition (X) may be irradiated with ultraviolet light in an oxygen-containing atmosphere such as an atmospheric atmosphere, or may be irradiated with ultraviolet light in an inert atmosphere such as a nitrogen atmosphere. In the present embodiment, since the oxygen content of the composition (X) is 75% by mass or less as described above, oxygen inhibition is less likely to occur even if the photopolymerizable compound (a) contains the radical polymerizable compound (a 1). Therefore, even when the composition (X) is irradiated with ultraviolet light in an oxygen-containing atmosphere, the composition (X) is easily cured.

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

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

Subsequently, ultraviolet rays are externally irradiated to the transparent substrate 3. The ultraviolet rays pass through the transparent substrate 3 and reach the ultraviolet-curable resin material. Thereby, the ultraviolet curable resin material is cured to produce the second sealing material 52.

In the present embodiment, as described above, a decrease in light emission efficiency due to the passivation layer 6 and the sealing material 5 in the light-emitting device 1 can be made less likely to occur.

The thickness of the sealing material 5 is, for example, 1 μm or more and 20 μm or less. The thickness of the sealing material 5 may be 15 μm or less. In this case, the light-emitting device 1 can be made thin and light by thinning the sealing material 5, and the light-emitting device 1 having flexibility can be obtained. Even if the thickness of the sealing material 5 is 10 μm or less, in the present embodiment, a decrease in light emission efficiency due to the passivation layer 6 and the sealing material 5 in the light emitting device 1 is less likely to occur. The thickness of the sealing material 5 is more preferably 8 μm or less. In order to effectively suppress the moisture from reaching the light-emitting element 4 with the sealing material 5, the thickness of the sealing material 5 is preferably 3 μm or more, and more preferably 5 μm or more.

The thickness of the passivation layer 6 overlapping the sealing material 5 is, for example, 0.1 μm or more and 2 μm or less. In the case where 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 preferably 0.1 μm or more and 2 μm or less.

The application of the composition (X) of the present embodiment is not limited to the production of the sealing material 5 for the light-emitting element 4. The composition (X) can be used for producing various optical members for transmitting light emitted from 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). The color filter may be provided in a display device such as an organic EL display, a micro LED display, or the like as a light emitting device.

[ examples ] A method for producing a compound

1. Preparation of the composition

The compositions of the examples and comparative examples were prepared by mixing the ingredients shown in the following table.

The components shown in the table are described in detail below. The viscosity of each of the following components was measured at 25 ℃ and a shear rate of 1000s using a rheometer (model DHR-2 manufactured by Anton Paar Japan)^-1The value measured under the conditions of (1).

Acryloyl morpholine, viscosity 12 mPas.

-morpholin-4-yl acrylate: viscosity 16 mPas.

Polyethylene glycol 200 dimethacrylate: viscosity 14 mPas, manufactured by Mizhongcun chemical industry.

-tripropylene glycol diacrylate: viscosity 15 mPas.

Pentaerythritol tetraacrylate: the viscosity was 350 mPas.

Irgacure TPO: 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide manufactured by BASF, having an absorption coefficient of 165 ml/g-cm for light having a wavelength of 405nm, and having photobleaching properties.

Irgacure 819: manufactured by BASF, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, has an absorption coefficient of 900 ml/g.cm for light having a wavelength of 405nm, and is photobleachable.

-Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one manufactured by BASF, an absorption coefficient of 0ml/g cm for light having a wavelength of 405nm, and no photobleaching property.

-Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by BASF corporation, has an absorption coefficient of 0 ml/g.em for light with a wavelength of 405nm, and has no photobleaching property.

-sensitizer 1: an anthracene-based sensitizer manufactured by Kawasaki chemical industry Co., Ltd., trade name ANTHRACURE (registered trademark) UVS-581.

-sensitizer 2: thioxanthone-based sensitizer, 2, 4-diethylthioxanthone, manufactured by Nippon Chemicals, under the trade name KAYACURE DETX-S.

Leveling agent 1: 2, 2-dimethoxy-1-phenyl-1-aza-2-silacyclopentane.

Leveling agent 2: 2, 2-dimethoxy-1-tetradecyl-1-aza-2-silacyclopentane.

Leveling agent 3: phenyltrimethoxysilane, available from shin Etsu chemical Co., Ltd., trade name KBM-103.

Leveling agent 4: hexyltriethoxysilane, manufactured by shin Etsu chemical Co., Ltd., product name KBM-3063.

2. Evaluation test

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

(1) Viscosity of the oil

The shear rate was 1000 seconds at 25 ℃ using a rheometer (model DHR-2 manufactured by Anton Paar Japan)^-1The viscosity of the composition was measured under the conditions of (1).

(2) Ink-jet property

The composition was charged into an ink cartridge of an ink jet printer (model DMP2831, manufactured by FUJIFILM), and droplets of the composition were ejected from a nozzle of the ink jet printer at a temperature of 30 ℃ and a frequency of 1 kHz. The liquid droplets were observed with a high-speed camera, and the case where neither ink mist nor splash was observed was evaluated as "a", and the case where at least one of ink mist and splash was observed was evaluated as "B".

(3) Transmittance of light

A coating film having a thickness of 10 μm was formed by coating the composition, and the coating film was irradiated with an LED-UV irradiator (model E075IIHD, peak wavelength 395nm) manufactured by Ushio corporation at 3W/cm in the air²The coating film was irradiated with ultraviolet rays for 5.3 seconds at the irradiation intensity of (2), and then heated at 100 ℃ for 5 minutes, thereby producing a film. The total light transmittance of the film was measured in accordance with JIS K7361-1.

(4) Rate of reaction

The composition was measured by an infrared spectrometer (model Agilent Cary610 FTIR microscope system, manufactured by Agilent Technologies) to obtain an IR spectrum.

A coating film having a thickness of 10 μm was formed by coating the composition, and the coating film was irradiated with a UV irradiation device (model CKL-200, CCS Co., Ltd.) at an irradiation intensity of 3W/cm²And the accumulated light amount is 0.9J/cm²The coating film was irradiated with ultraviolet rays having a peak wavelength of 395 nm. Next, the composition (cured product) irradiated with ultraviolet rays was measured by the infrared spectrometer, and an IR spectrum was obtained.

In both IR spectra, the measurement was carried out at 810cm^-1Peak intensity of absorption of the acryloyl group occurred. According to the peak intensity I of the coating film₀And the peak strength I of the cured product₁Using {1- (I)₀-I₁)/I₀The percentage of decrease in the reactive functional group ((meth) acryloyl group) in the composition before and after the irradiation with ultraviolet light was calculated according to the formula } × 100 (%). The result was regarded as the reaction rate.

(5) Difference in shrinkage rate

The composition had a thickness of 10 μm, a peak wavelength of 395nm and an irradiation intensity of 7W/cm in a UV irradiator (model CKL-200, manufactured by CCS Co., Ltd.)²And the accumulated light amount is 2.1J/cm²The curing shrinkage of the composition was calculated by measuring the curing shrinkage of the ultraviolet-curable resin according to JIS K6941.

Changing the irradiation condition of the ultraviolet rays to an irradiation intensity of 3W/cm²And the accumulated light amount is 0.9J/cm²Otherwise, the same operation is performedThe curing shrinkage of the composition was calculated.

The absolute value of the difference between the two cure shrinkage ratios obtained above was calculated.

(6) Uneven stripe

A coating film having a thickness of 10 μm was formed by applying the composition onto a quartz glass plate (50 mm. times.25 mm. times.1 mm in size) having a silicon oxynitride film (SiON film) formed on the surface thereof by a plasma CVD method. Under the atmosphere, model Unijet E075IIHD (peak wavelength 395nm) manufactured by Ushio motor was used, and the irradiation intensity was 5W/cm²And a cumulative light amount of 3000mJ/cm²The coating film was irradiated with ultraviolet rays under the conditions of (1) and cured to obtain a cured film.

The surface of the cured film was visually observed, and the case where no streaky unevenness was observed in the cured film was evaluated as "a", the case where streaky unevenness was observed in a region of less than 10% of the surface of the cured film was evaluated as "B", and the case where streaky unevenness was observed in a region of 10% or more of the surface of the cured film was evaluated as "C".

[ TABLE 1 ]

Claims

1. An ultraviolet-curable resin composition comprising a photopolymerizable compound A and a photopolymerization initiator B,

a coating film having a thickness of 10 μm was formed from the above ultraviolet-curable resin composition, and the irradiation intensity was 7W/cm²And the accumulated light amount is 2.1J/cm²Under the conditions of (1) a curing shrinkage ratio when the coating film is irradiated with ultraviolet rays having a wavelength region of any wavelength from 385 to 405nm at a peak wavelength, and an irradiation intensity of 3W/cm²And the accumulated light amount is 0.9J/cm²Under the condition (2) is not more than 2 percentage points in absolute value of difference of curing shrinkage rate when the ultraviolet ray is irradiated.

2. The ultraviolet-curable resin composition according to claim 1,a coating film having a thickness of 10 μm was formed from the above ultraviolet-curable resin composition, and the irradiation intensity was 3W/cm²And the accumulated light amount is 0.9J/cm²Under the condition (2), the reaction rate of the photopolymerizable compound A is 80% or more when the coating film is irradiated with ultraviolet rays having a peak wavelength of 395 nm.

3. The ultraviolet-curable resin composition according to claim 1 or 2, wherein the photopolymerizable compound a comprises a radical polymerizable compound a 1.

4. The ultraviolet-curable resin composition according to claim 3, wherein the radically polymerizable compound A1 contains an acrylic compound Y.

5. The ultraviolet-curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator B comprises a photobleachable photopolymerization initiator B3, and the percentage of the photopolymerization initiator B3 relative to the photopolymerization initiator B is 50% by mass or more.

6. The ultraviolet-curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator B comprises a photopolymerization initiator B4 having an absorption coefficient of 5 ml/g-cm or more for light having a wavelength of 405nm, and the percentage of the photopolymerization initiator B4 relative to the photopolymerization initiator B is 50% by mass or more.

7. The ultraviolet-curable resin composition according to claim 1 or 2, further comprising a sensitizer C, wherein the percentage of the sensitizer C with respect to the ultraviolet-curable resin composition is 0.05% by mass or more.

8. The ultraviolet-curable resin composition according to claim 1 or 2, further comprising a leveling agent D, wherein the percentage of the leveling agent D with respect to the ultraviolet-curable resin composition is 0.1% by mass or more.

9. The ultraviolet-curable resin composition according to claim 1 or 2, which is used for producing an optical component that transmits light emitted from a light source.

10. The ultraviolet-curable resin composition according to claim 1 or 2, which is formed by an ink jet method.

11. The ultraviolet-curable resin composition according to claim 1 or 2, wherein at least one of the viscosity at 25 ℃ and the viscosity at 40 ℃ is 30 mPas or less.

12. An optical member comprising a cured product of the ultraviolet-curable resin composition according to any one of claims 1 to 11.

13. A method of manufacturing an optical component, comprising: the ultraviolet-curable resin composition according to any one of claims 1 to 11 is molded by an ink jet method, and then irradiated with ultraviolet rays to be cured.

14. A light-emitting device comprising a light source and an optical member for transmitting light emitted from the light source, wherein the optical member comprises a cured product of the ultraviolet-curable resin composition according to any one of claims 1 to 11.

15. A method for manufacturing a light-emitting device including a light source and an optical member for transmitting light emitted from the light source,

the manufacturing method includes a step of manufacturing the optical member by the method of claim 13.