JP7442121B2 - Ultraviolet curable resin composition, color resist, color filter, light emitting device, and method for producing color resist - Google Patents

Description

The present invention relates to an ultraviolet curable resin composition, a color resist, a color filter, a light emitting device, and a method for producing a color resist, and specifically relates to an ultraviolet curable resin composition containing a phosphor (C), and this ultraviolet curable resin. The present invention relates to a color resist made from a composition, a color filter including the color resist, a light emitting device including the color filter, and a method for manufacturing the color resist.

2. Description of the Related Art Light-emitting devices including light-emitting elements such as light-emitting diodes are used in lighting applications, display applications, and the like, and are expected to become more popular in the future.

For example, Patent Document 1 discloses a liquid crystal display device having a backlight section using quantum dots.

Japanese Patent Application Publication No. 2010-191424

The inventor has been conducting research and development on a color resist containing a phosphor (C) such as a quantum dot. According to the findings obtained, if light-diffusing particles such as titanium oxide are incorporated into a color resist to scatter light within the color resist, it is expected that the efficiency of wavelength conversion of light by the color resist will be improved. However, the particles tend to settle in the composition for preparing the color resist, which impairs the storage stability of the composition.

An object of the present invention is to provide an ultraviolet curable resin composition that easily increases the wavelength conversion efficiency of light when a cured product is irradiated with light and that does not easily impair storage stability. An object of the present invention is to provide a color resist, a color filter including the color resist, a light emitting device including the color filter, and a method for manufacturing the color resist.

The ultraviolet curable resin composition according to one embodiment of the present invention contains a photopolymerizable compound (A), a photopolymerization initiator (B), a phosphor (C), and hollow particles (D).

A color resist according to one embodiment of the present invention includes a cured product of the ultraviolet curable resin composition.

A color filter according to one aspect of the present invention includes the color resist.

A light emitting device according to one aspect of the present invention includes the color filter and a light source that irradiates light to the color filter.

In the method for manufacturing a color resist according to one aspect of the present invention, the ultraviolet curable resin composition is molded by an inkjet method, and then the ultraviolet curable resin composition is cured by irradiating ultraviolet rays.

According to one aspect of the present invention, there is provided an ultraviolet curable resin composition that easily increases the wavelength conversion efficiency of light when a cured product is irradiated with light, and that does not easily impair storage stability; The produced color resist, a color filter provided with this color resist, a light emitting device provided with this color filter, and a manufacturing method of this color resist can be provided.

FIG. 1A is a schematic cross-sectional view of an example of a liquid crystal display device according to an embodiment of the present invention, and FIG. 1B is a schematic cross-sectional view of an example of an LED display device according to an embodiment of the present invention.

An embodiment of the present invention will be described below.

The ultraviolet curable resin composition according to this embodiment (hereinafter also referred to as composition (X)) includes a photopolymerizable compound (A), a photoinitiator (B), a phosphor (C), and a hollow particle (D ).

According to this embodiment, by molding the composition (X) and then curing it, a cured product having a light wavelength conversion function can be produced. This cured product can be applied, for example, to the color resist 1 in the color filter 2 (see FIGS. 1A and 1B). That is, according to this embodiment, a color filter 2 including a color resist 1 containing a phosphor (C) can be manufactured.

In this embodiment, since there is no need to heat the composition (X) when curing it, it is possible to prevent the light source, etc. in the light emitting device 11 from being damaged by heat, especially when producing the color filter 2 in the light emitting device 11.

Furthermore, in this embodiment, when the cured product of the composition (X) is irradiated with light, the hollow particles (D) can scatter the light within the cured product. Therefore, there are many opportunities for light to reach the phosphor (C) within the cured product, and as a result, the efficiency of wavelength conversion increases. Therefore, the cured product can exhibit high wavelength conversion efficiency compared to its size.

In this embodiment, the composition (X) is preferably molded by an inkjet method. In this case, it is easy to produce the color resist 1 with good positional accuracy. Furthermore, for this reason, it is easy to make the color resist 1 in the color filter 2 highly precise, that is, it is easy to produce minute color resist 1 with high density. Therefore, it is easy to achieve higher definition (higher resolution) of the light emitting device 11 including the color filter 2, especially the display device. In addition, when molding the composition (X) by an inkjet method, foreign substances are less likely to get mixed into the composition (X) and its cured product, compared to molding by a printing method that involves contact such as screen printing. Therefore, the yield in producing the color resist 1 is less likely to deteriorate.

When the composition (X) is molded by an inkjet method, it is difficult to increase the thickness of the color resist 1 produced from the composition (X), so the thickness of the color resist 1 is, for example, 10 μm or less. However, in this embodiment, as described above, the cured product of the composition (X) can exhibit high wavelength conversion efficiency compared to its size, so even if the thickness of the color resist 1 is small, the cured product of composition (X) can exhibit high wavelength conversion efficiency. Cheap.

It is preferable that the composition (X) does not contain a solvent or that the content of the solvent (the percentage of the solvent to the entire composition (X)) is 1% by mass or less. In this case, the composition (X) and the cured product of the composition (X) are unlikely to generate outgas derived from the solvent. Therefore, changes in the viscosity of the composition (X) due to volatilization of the solvent are less likely to occur, thereby increasing the storage stability of the composition (X). Further, it is possible to prevent the formation of voids caused by outgas in the color filter 2. Therefore, water is less likely to reach the color resist 1 through the voids, and the quantum dot phosphor (C1) in the color resist 1 is less likely to be degraded by water. Furthermore, a drying step for removing the solvent from the composition (X) and the cured product can be made unnecessary when producing the color resist 1. There may be a drying step for removing the solvent from at least one of the composition (X) and the cured product, but in this case, at least one of the heating temperature and heating time in the drying step can be reduced. It can be done. Therefore, outgassing from the color resist 1 can be suppressed without reducing the manufacturing efficiency of the color filter 2. Furthermore, if the composition (X) does not contain a solvent or the content of the solvent is 1% by mass or less, when the composition (X) is particularly molded by an inkjet method, the composition (X) after molding may be ) The thickness of the color resist 1 is less likely to decrease due to volatilization of the solvent, and therefore the color resist 1 is less likely to decrease in thickness. Therefore, while molding by the inkjet method, the thickness of the color resist 1 can be ensured as large as possible, and the wavelength conversion ability of the color resist 1 can be ensured as large as possible. The content of the solvent is more preferably 0.5% by mass or less, even more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferred that the composition (X) contains no solvent or only an unavoidably mixed solvent.

The glass transition temperature of the cured product of composition (X) is preferably 80°C or higher. That is, the composition (X) preferably has the property of becoming a cured product having a glass transition temperature of 80° C. or higher when cured. In this case, the cured product can have good heat resistance. Therefore, for example, when a cured product is subjected to a treatment that causes a rise in temperature, the cured product is unlikely to deteriorate. For this reason, for example, when the protective layer 5 is produced by a vapor deposition method such as a plasma CVD method so as to cover the color resist 1 produced from the composition (X), even if the color resist 1 is heated, the color resist 1 will deteriorate. Hateful. Furthermore, by increasing the heat resistance, the color resist 1 can be adapted to in-vehicle applications where heat resistance is strictly required. The glass transition temperature of the cured product is more preferably 90°C or higher, and even more preferably 100°C or higher. This glass transition temperature of the cured product can be achieved by the composition of composition (X) described in detail below.

The viscosity of composition (X) at 25° C. is preferably 30 mPa·s or less. In this case, the composition (X) can be easily molded by an inkjet method at room temperature. This viscosity is more preferably 25 mPa·s or less, even more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. It is also preferable that this viscosity is 1 mPa·s or more, and it is also preferable that this viscosity is 5 mPa·s or more.

It is also preferable that the viscosity of the composition (X) at 40° C. is 1 mPa·s or more and 30 mPa·s or less. In this case, whatever the viscosity of composition (X) at room temperature, it is possible to lower the viscosity by slightly heating composition (X). Therefore, by heating, composition (X) can be easily molded by an inkjet method. Furthermore, since the viscosity of the composition (X) can be lowered without significantly heating it, changes in the composition of the composition (X) due to volatilization of components in the composition (X) can be made less likely to occur. This viscosity is more preferably 25 mPa·s or less, even more preferably 20 mPa·s or less, and particularly preferably 15 mPa·s or less. It is also preferable that this viscosity is 5 mPa·s or more.

Such a low viscosity of composition (X) at 25°C or 40°C can be achieved by the composition of composition (X) as explained in detail below.

The volatility when 20 mg of composition (X) is heated at 100° C. for 30 minutes using a thermogravimetric analyzer is preferably 40% or less. The volatility of composition (X) is defined as the amount of weight loss of composition (X) after treatment with respect to the weight of composition (X) before treatment (the weight of composition (X) before treatment and after treatment). (difference from weight). In this case, the storage stability of composition (X) can be improved due to the low volatility of composition (X). Furthermore, outgassing is less likely to occur in the cured product of composition (X) and from the color resist 1. Therefore, voids caused by outgas are less likely to occur in the color filter 2. The volatility of composition (X) was determined by heating 20 mg of composition (X) using a thermogravimetric analyzer at 100°C for 30 minutes, and calculating the weight loss after treatment with respect to the weight before treatment. It can be obtained by calculating. The volatility when 20 mg of composition (X) is heated at 100°C for 30 minutes using a thermogravimetric analyzer is more preferably 30% or less, and if it is 20% or less, it is more preferable. The lower limit of volatility of composition (X) is not particularly limited, but may be, for example, 0.1% or more.

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

First, the phosphor (C) will be explained. It is preferable that the phosphor (C) contains a quantum dot phosphor (C1). When the phosphor (C) contains the quantum dot phosphor (C1), the color resist 1 produced from the composition (X) not only exhibits the same wavelength conversion function as a normal color resist, but also has a color It is easy to widen the color gamut of light emitted from the filter 2. Therefore, it is easy to realize a wide color gamut of light emitted from the light emitting device 11 including the color filter 2, especially the display device. Further, since the color filter 2 can realize a wide color gamut, there is no need to separately provide a member such as a filter for widening the color gamut in the light emitting device 11, especially the display device. Therefore, it is possible to suppress an increase in the number of parts of the light emitting device 11 (display device) when widening the color gamut. Therefore, it is possible to reduce the thickness of the light emitting device 11 (display device), and it is easy to realize, for example, a bendable and flexible light emitting device 11 (display device).

A quantum dot is a semiconductor particle that exhibits a quantum size effect, and a quantum dot phosphor (C1) is a phosphor (C) made of quantum dots. The average particle size of the quantum dot phosphor (C1) is, for example, 1 nm or more and 10 nm or less. The average particle size of the quantum dot phosphor (C1) is preferably 2 nm or more and 6 nm or less. Note that even if the quantum dot phosphors (C1) have the same composition, the wavelength of the fluorescence emitted will be different if the particle size is different. Therefore, the quantum dot phosphor (C1) preferably has a particle size that corresponds to the wavelength of fluorescence emitted by the color resist 1 produced from the composition (X). The quantum dot phosphor (C1) contains at least one type of semiconductor particle selected from the group consisting of semiconductor particles that emit red fluorescence, semiconductor particles that emit green fluorescence, and semiconductor particles that emit blue fluorescence, for example. do. The quantum dot phosphor (C1) may contain semiconductor particles that emit fluorescence of colors other than these.

Note that the average particle diameter of the quantum dot phosphor (C1) is the median diameter calculated from the measurement results by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As a measuring device, Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

The quantum dot phosphor (C1) may contain semiconductor particles having a core-shell structure. Specifically, the quantum dot phosphor (C1) contains semiconductor particles (CdSe/ZnS) having a core made of CdSe and a shell made of ZnS, for example. The quantum dot phosphor (C1) may contain other appropriate semiconductor particles. For example, the quantum dot phosphor (C1) includes GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO, CdS, and perovskite semiconductors. and graphene type semiconductors. Note that the semiconductor particles that can be included in the quantum dot phosphor (C1) are not limited to those described above.

The amount of the quantum dot phosphor (C1) in the composition (X) is, for example, 0.1% by mass or more and 40% by mass or less based on the entire composition (X). When the amount of the quantum dot phosphor (C1) is 0.1% by mass or more, the cured product of the composition (X) easily exhibits a wavelength conversion function. Further, if the amount of the quantum dot phosphor (C1) is 40% by mass or less, the composition (X) can be easily molded by an inkjet method. The amount of the quantum dot phosphor (C1) is more preferably 1% by mass or more, even more preferably 2% by mass or more, and particularly preferably 3% by mass or more. Further, the amount of the quantum dot phosphor (C1) is more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

Next, the hollow particles (D) will be explained. The hollow particle (D) has a shell portion and a hollow portion inside the shell portion, and thereby has an interface with a refractive index difference inside. Therefore, the hollow particles (D) tend to scatter light. Further, the hollow particles (D) have a small specific gravity due to having a hollow portion, and therefore are difficult to settle in the composition (X). Therefore, the hollow particles (D) do not easily impair the storage stability of the composition (X).

The median diameter of the hollow particles (D) is preferably 100 nm or more and 3 μm or less. When the median diameter is 100 nm or more, the hollow particles (D) tend to scatter light effectively. When the median diameter is 3 μm or less, damage to the inkjet device due to clogging or adhesion of the composition (X) within the inkjet device can be suppressed. This median diameter is more preferably 150 nm or more, and even more preferably 1 μm or more. Moreover, this median diameter is more preferably 800 nm or less, and even more preferably 500 nm or less. Note that the median diameter of the hollow particles (D) is calculated from the results of measurement by a dynamic light scattering method. As a measuring device, Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used.

The specific gravity of the hollow particles (D) is preferably 0.2 or more and 1.2 or less. When the specific gravity is 1.2 or less, the hollow particles (D) are particularly difficult to settle in the composition (X), and therefore the storage stability of the composition (X) is not particularly likely to be impaired. In addition, when the specific gravity is 0.4 or more, the phenomenon of floating on the surface during curing is eliminated and the composition is easily made uniform, and the physical strength is increased and damage to the hollow particles is reduced. The specific gravity is more preferably 1.0 or less, and even more preferably 0.8 or less. Further, the specific gravity is more preferably 0.3 or more, and even more preferably 0.4 or more.

The content ratio of the hollow particles (D), that is, the ratio of the hollow particles (D) to the total solid content of the composition (X) is preferably 0.1% by mass or more and 5% by mass or less. When this ratio is 0.1% by mass or more, the hollow particles (D) tend to scatter light more effectively. When this proportion is 5% by mass or less, composition (X) tends to have good inkjet properties. This proportion is more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. Further, this proportion is more preferably 4% by mass or less, and even more preferably 3% by mass or less.

The hollow particles (D) preferably contain at least one of organic resin particles (hereinafter referred to as hollow resin particles) and silica particles (hereinafter referred to as hollow silica particles). In this case, the light transmittance of the cured product is less likely to be impaired by the hollow particles (D).

It is particularly preferable that the hollow particles (D) include hollow resin particles. Hollow resin particles are less likely to break when force is applied than hollow silica particles. Therefore, even if force is applied to the hollow resin particles during the process such as kneading when preparing the composition (X) containing hollow resin particles or during the process of producing a cured product from the composition (X), the hollow resin particles will be damaged. It's hard to do. Moreover, the hollow resin particles are less likely to impair the storage stability of the composition (X). The hollow resin particles are made of acrylic resin, for example, and are, for example, hollow acrylic particles.

The photopolymerizable compound (A) is a component that can undergo a polymerization reaction upon irradiation with ultraviolet rays in the presence or absence of the photopolymerization initiator (B). The photopolymerization initiator (B) may also 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, for example, at least one of the radically polymerizable compound (A1) and the cationic polymerizable compound (W). When the photopolymerizable compound (A) contains a radically polymerizable compound (A1), the composition (X) preferably further contains a photoradical polymerization initiator (B1) as the photopolymerization initiator (B). . When the photopolymerizable compound (A) contains a cationic polymerizable compound (W), the composition (X) contains a photocationic polymerization initiator (B2) (cationic curing catalyst) as the photoinitiator (B). It is preferable to further contain it.

When the photopolymerizable compound (A) contains a radically polymerizable compound (A1), 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 entire acrylic compound (Y) at 25° C. is preferably 50 mPa·s or less. In this case, the acrylic compound (Y) can particularly reduce the viscosity of the composition (X). The viscosity of the acrylic compound (Y) as a whole is more preferably 30 mPa·s or less, particularly preferably 20 mPa·s or less. Further, the viscosity of the entire acrylic compound (Y) is, for example, 3 mPa·s or more.

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

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

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

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

The component having a viscosity of 20 mPa·s or less at 25°C preferably contains a compound having a glass transition temperature of 80°C or higher. In this case, the glass transition temperature of the cured product can be increased while reducing the viscosity of the composition (X). It is more preferable that this component contains a compound having a glass transition temperature of 90°C or higher, and even more preferably a compound having a glass transition temperature of 100°C or higher. There is no upper limit to the glass transition temperature of the compound contained in this component, but it is, for example, 150° C. or lower.

Compounds that can be included in the acrylic compound (Y) will be 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 can increase the heat resistance of the cured product. The proportion of the polyfunctional acrylic compound (Y1) is preferably 50% by mass or more and 100% by mass or less based on the entire acrylic compound (Y). The acrylic compound (Y) may contain only the polyfunctional acrylic compound (Y1).

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

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

It is preferable that the polyfunctional acrylic compound (Y1) contains a compound (Y11) having a structure shown in the following formula (200).

CH ₂ =CR ¹ -COO-(R ³ -O) _n -CO-CR ² =CH ₂ ...(200)
In formula (200), each of R ¹ and R ² is hydrogen or a methyl group, n is an integer of 1 or more, R ³ is an alkylene group having 1 or more carbon atoms, and when n is 2 or more, A plurality of R ³ 's may be the same or different.

Compound (Y11) has the structure shown in formula (200), and in particular, because R ³ in formula (200) has 3 or more carbon atoms, it is difficult to increase the affinity of the cured product with water. Therefore, the phosphor (C) is not easily deteriorated by water. The number of carbon atoms in R ³ is, for example, 1 or more and 15 or less, preferably 3 or more and 15 or less. In addition, compound (Y11) has the structure shown in formula (200), in particular, by having two (meth)acryloyl groups in one molecule, it is possible to increase the glass transition temperature of the cured product. , it is possible to improve the heat resistance of the cured product. Further, n in formula (200) is, for example, an integer of 1 or more and 12 or less.

The percentage ratio 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 particularly difficult to increase. The percentage ratio of the compound (Y11) to the acrylic compound (Y) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

It is particularly preferable that compound (Y11) contains a component having a boiling point of 270°C or higher. That is, the acrylic compound (Y) preferably contains a component having the structure shown in formula (200) and having a boiling point of 270° C. or higher. In this case, the acrylic compound (Y) is unlikely to volatilize from the composition (X) during storage of the composition (X) or when the composition (X) is heated. Therefore, the storage stability of composition (X) is less likely to be impaired. Furthermore, even if the compound (Y11) remains unreacted in the cured product of the composition (X), outgassing due to the compound (Y11) is unlikely to occur from the cured product. Therefore, voids due to outgas are less likely to occur in the color filter 2. If there are voids in the color filter 2, there is a risk that moisture will enter the color resist 1 through the voids, but if the voids are difficult to form, moisture will not easily enter the color resist 1. Note that the boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and is determined, for example, by the method shown in Science of Petroleum, Vol. II. P. 1281 (1938). It is more preferable that compound (Y11) contains a component having a boiling point of 280° C. or higher.

The percentage ratio 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) is effectively enhanced, the generation of outgas from the cured product is effectively reduced, and the affinity of the cured product to water is particularly difficult to increase. The percentage ratio of the compound (Y11) to the acrylic compound (Y) is, for example, 100% by mass or less, or 95% by mass or less, preferably 80% by mass or less.

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

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

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

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

The alkylene oxide-modified alkylene glycol di(meth)acrylate contains, for example, propylene oxide-modified neopentyl glycol. Further, the alkylene oxide-modified alkylene glycol di(meth)acrylate includes, for example, product number EBECRYL145 manufactured by Daicel Corporation.

When the acrylic compound (Y) contains a compound (Y11) having the structure shown in formula (200), the compound (Y11) preferably does not contain a compound in which the value of n in formula (200) is 5 or more. . (R ³ -O) When _n is a polyethylene glycol skeleton, it is particularly preferable that a compound in which the value of n in formula (200) is greater than 5 is not included. Even if the compound (Y11) contains a compound in which the value of n in formula (200) is greater than 5, the percentage of the compound in which the value of n in formula (200) is greater than 5 relative to the acrylic compound (Y) is 20. It is preferably less than % by mass. Further, even when compound (Y11) contains a compound in which the value of n in formula (200) is greater than 5, it is preferable that compound (Y11) does not contain a compound in which the value of n is greater than 9, and the value of n is greater than 9. It is further preferred that no compounds with a value greater than 7 be included. In these cases, the viscosity of composition (X) is particularly unlikely to increase.

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

When the polyfunctional acrylic compound (Y1) contains polyalkylene glycol di(meth)acrylate, the ratio of the polyalkylene glycol di(meth)acrylate to the acrylic compound (Y) shall be 40% by mass or more and 80% by mass or less. is preferred. When the proportion of polyalkylene glycol di(meth)acrylate is 40% by mass or more, the viscosity of the composition (X) can be effectively reduced. When the proportion of polyalkylene glycol di(meth)acrylate is 80% by mass or less, the proportion of compounds having three or more (meth)acryloyl groups in the molecule increases, and the reactivity of composition (X) and The glass transition temperature of the cured product can be increased. This proportion is more preferably 42% by mass or more and 75% by mass or less, and even more preferably 45% by mass or more and 70% by mass or less.

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

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

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

The polyfunctional acrylic compound (Y1) may have at least one of a benzene ring, an alicyclic ring, and a polar group. The polar group is, for example, at least one of an OH group and an NHCO group. In this case, shrinkage when the composition (X) is cured can be particularly reduced. Furthermore, it is also possible to improve the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide. The polyfunctional acrylic compound (Y1) is in particular at least one selected from the group consisting of tricyclodecane dimethanol diacrylate, bisphenol A polyethoxy diacrylate, bisphenol F polyethoxy diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. It is preferable to contain one type of compound. These compounds can particularly reduce shrinkage when composition (X) is cured. Furthermore, these compounds can also improve the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide.

When the adhesion between the cured product and the inorganic material increases, when the color resist 1 is overlapped with a film made of an inorganic material (inorganic film) such as a SiN film, the adhesion between the color resist 1 and the inorganic film increases. is easy to obtain. Strictly speaking, since the adhesion between the resin matrix cured by the photopolymerizable compound (A) and the inorganic compound increases, when the phosphor (C) is an inorganic particle such as a quantum dot phosphor (C1), In this case, the adhesion between the resin matrix and the phosphor (C) tends to increase in the cured product.

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

It is also preferable that the acrylic compound (Y) contains a monofunctional acrylic compound (Y2) in which the radically polymerizable functional group in one molecule is only one (meth)acryloyl group. The monofunctional acrylic compound (Y2) can suppress shrinkage during curing of the composition (X).

The amount of the monofunctional acrylic compound (Y2) relative to the total amount of the acrylic compound (Y) is preferably greater than 0% by mass and not more than 50% by mass. If the amount of the monofunctional acrylic compound (Y2) is more than 0% by mass, shrinkage during curing of the composition (X) 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, which can particularly improve the heat resistance of the cured product. It is more preferable that the amount of the monofunctional acrylic compound (Y2) is 5% by mass or more, and even more preferably 30% by mass or less.

Examples of the monofunctional acrylic compound (Y2) include tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, and 2-methoxyethyl acrylate. , methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, Imide acrylate, isoamyl acrylate, ethoxylated succinic acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, Isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl/decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, Methoxypolyethylene glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl Acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloyl Morpholine, morpholin-4-yl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

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

Compounds having an alicyclic structure include, for example, phenoxyethyl acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butyl Cyclohexyl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, From acryloylmorpholine, morpholin-4-yl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate Contains at least one compound selected from the group consisting of:

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

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

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

The acrylic compound (Y) may contain a compound having nitrogen in its molecular skeleton. In this case, the adhesiveness between the cured product and the inorganic material is improved. In addition, the reactivity of the acrylic compound (Y) tends to improve, and therefore outgas is less likely to be generated from the cured product. The compound having nitrogen in its molecular skeleton is selected from the group consisting of compounds having a morpholine skeleton such as acryloylmorpholine, morpholin-4-yl acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidyl methacrylate. Contains at least one compound.

It is particularly preferable that the acrylic compound (Y) contains a compound having a morpholine skeleton. In this case, the reactivity of the composition (X) can be further improved, and the curability of the composition (X) in an atmospheric atmosphere can be further improved. It is particularly preferable that the acrylic compound (Y) contains at least one of acryloylmorpholine and morpholin-4-yl acrylate. In this case, shrinkage during curing of the composition (X) can be suppressed. Furthermore, the viscosity of acryloylmorpholine and morpholin-4-yl acrylate is low, and therefore, these compounds are difficult to increase the viscosity of composition (X). Furthermore, since these compounds are difficult to volatilize, the storage stability of composition (X) can be easily improved.

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

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

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

In formula (100), R ⁰ is H or a methyl group. X is a single bond or a divalent hydrocarbon group. Each of R ¹ to R ¹¹ is H, an alkyl group or -R ¹² -OH, R ¹² is an alkylene group, and at least one of R ¹ to R ¹¹ is an alkyl group or -R ¹² -OH. R ¹ to R ¹¹ are not chemically bonded to each other.

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

The radically polymerizable compound (A1) may contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radically polymerizable compound (Z) relative to the total amount of the acrylic compound (Y) and the radically polymerizable compound (Z) is, for example, 10% by mass or less. The radically polymerizable compound (Z) includes a polyfunctional radically polymerizable compound (Z1) having two or more radically polymerizable functional groups in one molecule, and a monofunctional radically polymerizable compound (Z1) having only one radically polymerizable functional group in one molecule. It can contain either one or both of the radically polymerizable compounds (Z2). The polyfunctional radically polymerizable compound (Z1) is, for example, a group consisting of aromatic urethane oligomers having two or more ethylenic double bonds in one molecule, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers. It may contain at least one kind of compound selected from. Note that the components that the polyfunctional radically polymerizable compound (Z1) may contain are not limited to the above. Examples of the monofunctional radically polymerizable compound (Z2) include N-vinylformamide, vinylcaprolactam, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene Contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone, and N-vinylcaprolactam. Note that the components that the monofunctional radically polymerizable compound (Z2) may contain are not limited to the above.

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

In other words, the radically polymerizable compound (A1) preferably contains a compound having nitrogen in its molecular skeleton. This compound having nitrogen in its molecular skeleton may contain a compound included in the acrylic compound (Y) or a compound included in the radically polymerizable compound (Z). In this case, the adhesiveness between the cured product and the inorganic material is improved. The proportion of the compound having nitrogen in its molecular skeleton with respect to the entire radically polymerizable compound (A1) is preferably 5% by mass or more and 80% by mass or less. When this proportion is 5% by mass or more, the adhesion between the cured product and the inorganic material is particularly likely to be improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton will hardly impede the storage stability of the composition (X), and the satellite when spraying the composition (X) by an inkjet method will be Hard to cause. Therefore, the inkjet properties of composition (X) are not easily inhibited. Furthermore, outgassing caused by compounds having nitrogen in the molecular skeleton can be made less likely to occur. This proportion is more preferably 10% by mass or more and 70% by mass or less, even 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.

The photoradical polymerization initiator (B1) is not particularly limited as long as it is a compound that generates radical species when irradiated with ultraviolet rays. Examples of the photoradical polymerization initiator (B1) include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole. compound, an oxime ester compound, a borate compound, an azinium compound, a metallocene compound, an active ester compound, a compound having a carbon-halogen bond, and an alkylamine compound. The amount of the photoradical polymerization initiator (B1) relative to 100 parts by weight of the composition (X) is, for example, 1 part by weight or more and 10 parts by weight or less.

It is preferable that the photoradical polymerization initiator (B1) contains an initiator having photobleaching properties. In this case, the light transmittance of the cured product tends to increase.

The initiator having photobleaching properties contains, for example, at least one of an oxime ester compound and an acylphosphine oxide compound having photobleaching properties.

The oxime ester compound having photobleaching properties contains, for example, at least one of a compound represented by the following formula (401) and a compound represented by the following formula (402). Among these, the compound represented by formula (402) has particularly high sensitivity, so it is particularly easy to enhance the photocurability of composition (X).

The acylphosphine oxide compound includes, for example, at least one selected from the group consisting of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide. contains.

The radical photopolymerization initiator (B1) may contain a sensitizer as a part of the radical photopolymerization initiator (B1). The sensitizer can promote the radical generation reaction of the photoradical polymerization initiator (B1), improve the reactivity of radical polymerization, and improve the crosslink density. Examples of the sensitizer include 9,10-dibutoxyanthracene, 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, 4,4'-bis(dimethylamino)benzophenone, It can contain at least one compound selected from the group consisting of 4,4'-bis(diethylamino)benzophenone, p-dimethylaminobenzaldehyde, and p-diethylaminobenzaldehyde. Note that the components that the sensitizer may contain are not limited to the above.

The content of the sensitizer in the composition (X) is, for example, 0.1 parts by mass or more and 5 parts by mass or less, preferably 0.1 parts by mass, based on 100 parts by mass of the solid content of the composition (X). Part or more and no more than 3 parts by mass. If the content of the sensitizer is within this range, the composition (X) can be cured in air, and it is not necessary to cure the composition (X) in an inert atmosphere such as a nitrogen atmosphere. It disappears.

Composition (X) may contain a polymerization accelerator in addition to the photoradical polymerization initiator (B1). Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl. Note that the components that the polymerization accelerator may contain are not limited to the above.

When the photopolymerizable compound (A) contains a cationically polymerizable compound (W), the cationically polymerizable compound (W) is, for example, a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). Contains at least one of the following.

The polyfunctional cationic polymerizable compound (W1) is either or both of a polyfunctional cationic polymerizable compound (W11) that does not have a siloxane skeleton and a polyfunctional cationic polymerizable compound (W12) that has a siloxane skeleton. can contain.

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

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

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

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

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

In formula (1), X is a single bond or a divalent organic group, and the organic group is, for example, -CO-O-CH ₂ -.

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

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

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

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

The polyfunctional heterocyclic epoxy compound contains, for example, a trifunctional epoxy compound as shown in the following formula (2).

The polyfunctional oxetane compound contains, for example, a bifunctional oxetane compound as shown in the following formula (3).

The alkylene glycol diglycidyl ether contains, for example, at least one compound selected from the group consisting of compounds shown in the following formulas (4) to (7).

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

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

It is also preferable that the polyfunctional cationic polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound. In this case, composition (X) can have particularly high cationic polymerization reactivity.

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

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

In addition, the compound represented by formula (20) in particular has a low viscosity, so when containing the compound represented by formula (20), composition (X) can have good ultraviolet curability and, in particular, Can have low viscosity. Furthermore, although the compound represented by formula (20) has a low viscosity, it has a property of being difficult to volatilize. Therefore, even if composition (X) contains the compound represented by formula (20), composition (X) is unlikely to change its composition due to volatilization of the compound represented by formula (20). Therefore, by containing the compound represented by formula (20), composition (X) can be made to have a low viscosity without impairing storage stability.

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

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

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

When the composition (X) contains a polyfunctional cationic polymerizable compound (W11), the proportion of the polyfunctional cationic polymerizable compound (W11) to the total amount of the resin component is preferably within the range of 5 to 95% by mass. . Note that the resin component refers to a compound having cationic polymerizability in the composition (X), and includes a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). When the proportion of the polyfunctional cationic polymerizable compound (W11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, and thereby the cured product has high strength. (hardness). Further, if the proportion of the polyfunctional cationic polymerizable compound (W11) is 95% by mass or less, when the composition (X) contains the hygroscopic agent (C), the hygroscopic agent (C) in the composition (X) ) can be particularly easily dispersed evenly. The proportion of this polyfunctional cationic polymerizable compound (W11) is preferably 12% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. Particularly preferred. Further, the proportion of this polyfunctional cationic polymerizable compound (W11) is more preferably 85% by mass or less, and even more preferably 60% by mass or less. For example, the proportion of the polyfunctional cationic polymerizable compound (W11) is preferably within the range of 20 to 60% by mass.

When the polyfunctional cationic polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of the polyfunctional cationic polymerizable compound (W11), or all of the polyfunctional cationically polymerizable compound (W11). It may be. The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (W11) is preferably within the range of 15 to 100% by mass. When this proportion is 15% by mass or more, the polyfunctional alicyclic epoxy compound can particularly contribute to improving the 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 cationically polymerizable functional groups per molecule of the polyfunctional cationically polymerizable compound (W12) is preferably 2 to 6, more preferably 2 to 4. The polyfunctional cationic polymerizable compound (W12) can contribute to improving the cationic polymerization reactivity of the composition (X), and can also contribute to improving the heat discoloration resistance of the cured product and optical components. The polyfunctional cationically polymerizable compound (W12) can also contribute to lowering the elastic modulus of cured products and optical components. When the composition (X) contains a hygroscopic agent, the polyfunctional cationic polymerizable compound (W12) can also contribute to improving the dispersibility of the hygroscopic agent in the composition (X) and in the cured product.

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

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

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

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

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

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

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

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) is, for example, product number X-40-2669, X-40-2670, X-40-2715, X-40-2732, X manufactured by Shin-Etsu Chemical Co., Ltd. -Containing at least one component selected from the group consisting of -22-169AS, X-22-169B, X-22-2046, X-22-343, X-22-163, and X-22-163B is preferred.

The polyfunctional cationic polymerizable compound (W12) preferably has an alicyclic epoxy structure, and it is particularly preferred if the polyfunctional cationic polymerizable compound (W12) contains a compound represented by formula (10a). The compound represented by formula (10a) can particularly contribute to improving the cationic polymerization reactivity and lowering the viscosity of the composition (X), and particularly contributes to improving the heat discoloration resistance and lowering the elastic modulus of cured products and optical components. I can contribute. When the composition (X) contains the hygroscopic agent (C), it can particularly contribute to improving the dispersibility of the hygroscopic agent (C) in the composition (X).

When the composition (X) contains a polyfunctional cationic polymerizable compound (W12), the ratio of the polyfunctional cationic polymerizable compound (W12) to the total amount of the resin component is preferably within the range of 5 to 95% by mass. . In this case, especially when the composition (X) contains the hygroscopic agent (C), the dispersibility of the hygroscopic agent (C) in the composition (X) and in the cured product is particularly improved, and the composition (X) can have particularly high photocationic 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 the group consisting of an epoxy group, an oxetane group, and a vinyl ether group.

The viscosity of the monofunctional cationic polymerizable compound (W2) at 25° C. is preferably 8 mPa·s 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 cationically polymerizable compound (W2) at 25° C. is preferably within the range of 0.1 to 8 mPa·s.

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

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

In addition, especially when the composition (X) contains a polyfunctional cationic polymerizable compound (W11) and a polyfunctional cationic polymerizable compound (W12), the polyfunctional cationic polymerizable compound (W11) is The proportion of the polyfunctional cationically polymerizable compound (W12) is within the range of 15 to 30% by mass, and the proportion of the monofunctional cationically polymerizable compound (W2) is within the range of 15 to 40% by mass. It is preferably within the range of %. In this case, good storage stability, low viscosity, and good cationic polymerization reactivity of composition (X) can be achieved in a well-balanced manner, and furthermore, excellent transparency, excellent hygroscopicity, and high refractive index of the cured product can be achieved. It can be achieved well.

If the cationic polymerizable compound (W) contains the compound shown in formula (3) and the compound shown in formula (16), a photocured product can be produced from the composition (X) by adjusting the ratio of both. In this case, it is possible to reduce the viscosity of the composition (X) and improve its storage stability while appropriately adjusting the ease with which the curing reaction progresses.

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

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

In formula (30), X is at least one selected from the group consisting of halogen, H, hydrocarbon group, and alkylene glycol group, and when there is a plurality of X in one molecule, they may be the same or different from each other. It's okay. Hydrocarbon groups are, for example, alkyl groups or aryl groups. When X is a hydrocarbon group, the number of carbon atoms in X is, for example, within the range of 1 to 10. R is a single bond or a divalent organic group. When R is a divalent organic group, the divalent organic group is, for example, an alkylene group, an oxyalkylene group, a carbonyloxyalkylene group (e.g. -CO-O-CH ₂ -), or -C(Ph) ₂ -O -CH ₂ - group. Y is H or a monovalent organic group. When Y is a monovalent organic group, the monovalent organic group is, for example, an alkyl group or an aryl group.

When the cationic polymerizable compound (W) contains the aromatic epoxy compound (f1), the aromatic epoxy compound (f1) has a low viscosity, so the aromatic epoxy compound (f1) lowers the viscosity of the composition (X). Easy to do. In addition, the aromatic epoxy compound (f1) is difficult to volatilize, so even if the composition (X) is stored, the composition (X) is unlikely to change its composition due to volatilization of the aromatic epoxy compound (f1). . Therefore, the aromatic epoxy compound (f1) tends to improve the storage stability of the composition (X). Further, since the aromatic epoxy compound (f1) has high reactivity, unreacted components are unlikely to remain in the cured product, and therefore outgas is unlikely to be generated from the cured product. Furthermore, the aromatic epoxy compound (f1) tends to increase the glass transition temperature of the cured product, and therefore tends to increase the heat resistance of the cured product.

Furthermore, the aromatic epoxy compound (f1) is less likely to produce defective droplets called satellites when the composition (X) is ejected by an inkjet method. A satellite is a droplet that separates from the original droplet and adheres to a position different from the original position of the droplet on the application target when the droplet is ejected using an inkjet method. If satellites are formed, the dimensional accuracy of the cured product produced from composition (X) will deteriorate.

It is preferable that R in formula (30) is a single bond or an alkylene group. When n in formula (30) is 2 or 3, it is preferable that at least one of the plurality of R's 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 therefore the curability of the composition (X) when irradiated with ultraviolet rays 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 formulas (301) to (318), respectively.

In particular, the aromatic epoxy compound (f1) may contain at least one component selected from the group consisting of compounds represented by formulas (301) to (305), (312), (314) and (318), respectively. preferable. These compounds tend to have high reactivity because at least one epoxy group (oxirane) and benzene ring in the compound are bonded by a single bond or an alkylene group, and therefore, the curing of composition (X) Easy to increase sex.

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

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

When the cationic polymerizable compound (W) contains the compound (f2), the compound (f2) has a low viscosity, so the compound (f2) tends to lower the viscosity of the composition (X). In addition, compound (f2) is difficult to volatilize, so even if composition (X) is stored, composition (X) is unlikely to change its composition due to volatilization of aromatic epoxy compound (f1). Therefore, compound (f2) tends to improve the storage stability of composition (X).

Furthermore, compound (f2) is less likely to produce defective droplets called satellites when the composition (X) is ejected by an inkjet method. Furthermore, compound (f2) makes it difficult to generate satellites even when the speed of droplets ejected by an inkjet method is increased. Therefore, depending on the inkjet conditions, for example, it is possible to increase the droplet ejection speed by the inkjet method to 4 m/s or more without producing satellites. If the speed of the droplet can be increased, the trajectory of the droplet will be less susceptible to disturbances, so the dimensional accuracy of the cured product produced from the composition (X) can be improved. Furthermore, as mentioned above, compound (f2) can improve the storage stability of composition (X), so even if composition (X) is stored for a long period of time, satellites are unlikely to occur. Characteristics are easily maintained.

It is particularly preferable that the oxyalkylene skeleton contains a structure "--C--C--O-", that is, an oxymethylene unit. In this case, satellites are particularly difficult to form, and even if the driving frequency for ejecting composition (X) by, for example, an inkjet method is varied, satellites are difficult to form. Further, the compound (f2) is less volatile and tends to have a lower viscosity, and furthermore, the affinity (wettability) of the composition (X) for the inorganic material tends to increase.

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

Note that a substituent other than hydrogen may be bonded to the oxyalkylene unit in the oxyalkylene skeleton of compound (f2). For example, the oxymethylene unit contained in the oxyalkylene skeleton may have the structure "-CH(CH ₃ )-CH ₂ --O-".

The proportion of the compound (f2) is preferably 10% by mass or more based on the cationically polymerizable compound (W). In this case, the inkjet property will be good and the wettability to the base material will be good.
It is also preferable that this proportion is 70% by weight or less. In this case, the glass transition temperature can be sufficiently increased. This proportion is more preferably 15% by mass or more and 60% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less.

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

Compound (f21) is, for example, a compound represented by the above formula (1b), a compound represented by formula (4), a compound represented by formula (5), a compound represented by formula (6), a compound represented by formula (7), or a compound represented by formula (7). It contains at least one compound selected from the group consisting of the compound shown in (8), the compound shown in formula (13), the compound shown in formula (14), and the like. Note that the components that compound (f21) may contain are not limited to the above.

Compound (f22) is, for example, at least one selected from the group consisting of the compound represented by the above formula (3), the compound represented by formula (12), the compound represented by formula (16), and the compound represented by formula (17). Contains the following compounds. Note that the components that can be contained in compound (f22) are not limited to those listed above.

The refractive index of the resin matrix produced by polymerization of the photopolymerizable compound (A) is preferably higher than the refractive index of the shell portion of the hollow particles (D). In this case, in the cured product of composition (X), light scattering is likely to occur even at the interface between the shell portion of the hollow particles and the resin matrix, and therefore the wavelength conversion ability of the color resist 1 is more likely to be enhanced. In this case, the difference in refractive index between the shell portion and the resin matrix is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.10 or more. In order to increase the refractive index of the resin matrix, for example, the photopolymerizable compound (A) is mixed with a compound having an aromatic ring, a compound having a halogen group other than fluorine, a compound having sulfur, and a compound having an alicyclic group. At least one compound selected from the group consisting of: When at least one selected from the group consisting of aromatic rings, fluorine atoms, sulfur atoms, and alicyclic groups is introduced into the resin matrix, the refractive index of the resin matrix tends to increase. Note that the refractive index of the resin matrix refers to the refractive index of the resin in Examples described later.

The sulfur-containing compound preferably has at least one ethylenically unsaturated group in one molecule and at least one sulfur atom in one molecule. The ethylenically unsaturated group may be a (meth)acryloyl group or a group other than the (meth)acryloyl group. It is particularly preferable that the sulfur-containing compound contains a compound having a phenyl sulfide skeleton. The phenyl sulfide skeleton refers to a structure in which a phenyl group and a sulfur atom are directly bonded through a single bond. The compound having a phenyl sulfide skeleton preferably contains a polyarylene sulfide compound. A polyarylene sulfide compound is a compound having a repeating unit represented by [-Ar-S-] in the molecule. Ar is an arylene group, for example a phenylene group. The sulfur-containing compound includes, for example, at least one selected from the group consisting of allyl phenyl sulfide, vinyl phenyl sulfide, bis(4-methacryloylthiophenyl) sulfide, and the like. In particular, it is preferable that the sulfur-containing compound contains bis(4-methacryloylthiophenyl) sulfide, which does not easily generate odor. The ratio of the compound having sulfur to the photopolymerizable compound (A) is, for example, 10% by mass or more and 90% by mass or less, preferably 25% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 80% by mass or less. .

Note that the refractive index of the resin matrix and the refractive index of the shell portion of the hollow particles (D) are the refractive indexes at 25° C. for light with a wavelength of 587.6 nm (d-line of helium).

It is also preferable that the cationic polymerizable compound (W) contains an epoxy compound and the above compound (f22). The epoxy compound contains at least one type of compound having an epoxy group among the compounds that can be included in the above-mentioned cationically polymerizable compound (W), for example. When the cationic polymerizable compound (W) contains an epoxy compound and a compound (f22), the curability of the composition (X) when the composition (X) is irradiated with ultraviolet rays tends to increase, and the composition at this time Too rapid curing of product (X) is less likely to occur, and therefore the cured product is less likely to suffer from deterioration in transparency due to cloudiness or the like. The mechanism that causes this effect is presumed to be as follows. Since the reactivity of the compound (f22) is lower than that of the epoxy compound, when the composition (X) is irradiated with ultraviolet rays, the epoxy compound reacts first. This reaction of the epoxy compound tends to increase the curability of the composition (X). Subsequently, the reaction of the compound (f22) makes it difficult for the epoxy compound and the compound (f22) to react at the same time. It is thought that this makes it difficult for an excessively rapid reaction to occur. In this case, the ratio of the compound (f22) to the cationically polymerizable compound (W) is preferably 20% by mass or more. In this case, the compound (f22) particularly tends to reduce the viscosity of the composition (X) and particularly tends to improve the storage stability of the composition (X). Furthermore, compound (f22) particularly tends to enhance the curability of composition (X). It is also preferable that the proportion of compound (f22) is 90% by mass or less. In this case, the curability of the cured product can be sufficiently improved. The proportion of compound (f22) is more preferably 10% by mass or more and 90% by mass or less, and even more preferably 20% by mass or more and 80% by mass or less. Further, 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 based on the total amount of the cationic polymerizable compound (W). , more preferably 25% by mass or more and 75% by mass or less. In these cases, the unreacted groups in the cured product can be sufficiently reduced to sufficiently increase the curability of the cured product.

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

It is particularly preferable that the cationic polymerizable compound (W) contains the compound (f2) and an epoxy compound, and the epoxy compound further contains the above-mentioned aromatic epoxy compound (f1). In this case, the composition (X) tends to have particularly excellent storage stability, and when the composition (X) is ejected by an inkjet method, defective droplets called satellites are hardly generated. Furthermore, even if the speed of droplets ejected by the inkjet method is increased, satellites are particularly difficult to form. Furthermore, even if composition (X) is stored for a long period of time, the property of composition (X) that it is difficult to form satellites is particularly easily maintained. In this case, it is particularly preferred if compound (f2) contains compound (f22).

The total ratio of the aromatic epoxy compound (f1) and the compound (f22) to the cationically polymerizable compound (W) 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 significant. This proportion is more preferably 60% by mass or more, and even more preferably 70% by mass or more. It is particularly preferable that the cationic polymerizable compound (W) contains only the aromatic epoxy compound (f1) and the compound (f22).

When the composition (X) contains the cationic polymerizable compound (W), it is preferable that the composition (X) further contains a sensitizer. In this case, composition (X) can have particularly high cationic polymerization reactivity. The sensitizer contains, for example, one or both of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene. The ratio of the sensitizer to the cationic polymerizable compound (W) is preferably greater than 0% by mass and 1% by mass or less. In this case, the sensitizer hardly inhibits the transparency of the cured product, and therefore the cured product can have good transparency.

When the composition (X) contains the cationically polymerizable compound (W), it is preferable that the composition (X) further contains a photocationic polymerization initiator (B2). The photocationic polymerization initiator (B2) is not particularly limited as long as it is a catalyst that generates a protonic acid or a Lewis acid upon irradiation with light. The photocationic polymerization initiator (B2) can contain at least one of an ionic photoacid-generating cationic curing catalyst and a nonionic photoacid-generating cationic curing catalyst.

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

The nonionic photoacid-generating cationic curing catalyst is, for example, at least one selected from the group consisting of nitrobenzyl esters, sulfonic acid derivatives, phosphoric esters, phenolsulfonic esters, diazonaphthoquinones, and N-hydroxyimide phosphonates. It can contain the following ingredients. Note that the components that can be contained in the nonionic photoacid generating type cation curing catalyst are not limited to the above.

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

The ratio of the photocationic polymerization initiator (B2) to the cationically polymerizable compound (W) is preferably within the range of 1 to 4% by mass. When this proportion is 1% by mass or more, composition (X) can have particularly good cationic polymerization reactivity. In addition, since this proportion is 4% by mass or less, the composition (X) can have good storage stability, and since it does not contain an excessive photocationic polymerization initiator (B2), manufacturing costs can be reduced. is possible.

Composition (X) may contain a dispersant (E). The dispersant (E) can improve the dispersibility of the phosphor (C) in the composition (X). Therefore, the dispersant (E) is less likely to cause an increase in viscosity and a decrease in storage stability of the composition (X) due to the phosphor (C).

Note that the dispersant (E) is a surfactant that can be adsorbed to particles. The dispersant (E) has an adsorption group (generally referred to as an anchor) that can be adsorbed to particles, and a molecular skeleton (generally referred to as a tail) that attaches to the particles by adsorption of the adsorption groups to the particles. Dispersants (E) include, for example, acrylic dispersants whose tails are acrylic molecular chains, urethane dispersants whose tails are urethane molecular chains, and polyester dispersants whose tails are polyester molecular chains. It contains at least one component selected from the group consisting of: The adsorption group includes, for example, at least one of a basic polar functional group and an acidic polar functional group. The basic polar functional group includes, for example, at least one group selected from the group consisting of an amino group, an imino group, an amide group, an imide group, and a nitrogen-containing heterocyclic group. The acidic polar functional group includes, for example, at least one group selected from the group consisting of a carboxyl group and a phosphoric acid group. The dispersant (E) is at least one compound selected from the group consisting of, for example, the Solspers series manufactured by Japan Louvre Sol Co., Ltd., the DISPERBYK series manufactured by BYK Chemie Japan Co., Ltd., and the Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd. can contain. Note that the components that the dispersant (E) may contain are not limited to the above.

The amount of the dispersant (E) relative to the phosphor (C) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (E) is 5 parts by mass or more, the function of the dispersant (E) can be effectively expressed, and when the amount is 60 parts by mass or less, the dispersant (E) in the color resist 1 can be effectively expressed. It is possible to suppress free molecules from interfering with the adhesion between the color resist 1 and the inorganic material member. Further, the amount of the dispersant (D) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, especially 30 parts by mass or less. preferable.

The dispersant (D) is added to the composition (X) if necessary. In cases where the phosphor (C) has been subjected to surface treatment to improve dispersibility, the phosphor (C) may be well-formed even if the composition (X) does not contain the dispersant (E). It can be dispersed.

As described above, in this embodiment, composition (X) preferably does not contain a solvent or has a solvent content of 1% by mass or less. Therefore, outgassing is less likely to occur from the composition (X) and the cured product. Moreover, the storage stability of composition (X) is further improved.

Composition (X) can be prepared by mixing the above-mentioned components. Composition (X) is preferably liquid at 25°C.

Composition (X) may further contain a moisture absorbent (F). When the composition (X) contains the hygroscopic agent (F), even if the cured product of the composition (X) and the color resist 1 are exposed to moisture, the hygroscopic agent (F) absorbs the moisture and the cured product And the quantum dot phosphor (C1) in the color resist 1 becomes less likely to deteriorate. The average particle size of the moisture absorbent (F) is preferably 200 nm or less. In this case, the cured product can have high transparency.

The moisture absorbent (F) is preferably an inorganic particle having hygroscopicity, and contains at least one component selected from the group consisting of, for example, zeolite particles, silica gel particles, calcium chloride particles, and titanium oxide nanotube particles. is preferred. Note that the components that the moisture absorbent (F) may contain are not limited to the above. It is particularly preferred that the moisture absorbent (F) contains zeolite particles.

Zeolite particles having an average particle size of 200 nm or less can be produced, for example, by crushing common industrial zeolite. In producing zeolite particles, the zeolite may be pulverized and then crystallized by hydrothermal synthesis or the like, in which case the zeolite particles can have particularly high hygroscopicity. Examples of methods for producing such zeolite particles are disclosed in JP-A No. 2016-69266, JP-A No. 2013-049602, and the like.

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

The average particle size of the moisture absorbent (F) is preferably 10 nm or more and 200 nm or less. If this average particle size is 200 nm or less, the cured product can have particularly high transparency. Moreover, if this average particle diameter is 10 nm or more, good hygroscopicity of the hygroscopic agent (F) can be maintained. Note that this average particle diameter is the median diameter calculated from the measurement results by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). Note that the Nanotrac Wave series manufactured by Microtrac Bell Co., Ltd. can be used as the measuring device.

The average particle size of the moisture absorbent (F) is more preferably 150 nm or less, even more preferably 100 nm or less, and particularly preferably 70 nm or less. Further, the average particle size of the moisture absorbent (F) is preferably 20 nm or more, more preferably 50 nm or more. In this case, the cured product can have particularly good transparency and hygroscopicity.

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

When the composition (X) contains a hygroscopic agent (F), the proportion of the hygroscopic agent (F) to the total amount of the composition (X) is preferably 1% by mass or more and 20% by mass or less. If the proportion of the hygroscopic agent (F) is 1% by mass or more, the cured product can have particularly high hygroscopicity. Further, if the proportion of the moisture absorbent (F) is 20% by mass or less, the viscosity of the composition (X) can be particularly reduced, and the composition (X) has a sufficiently low viscosity that it can be coated by an inkjet method. You can also do it. The proportion of the moisture absorbent (F) is more preferably 3% by mass or more, particularly preferably 5% by mass or more. Further, the proportion of the moisture absorbent (F) is more preferably 15% by mass or less, particularly preferably 13% by mass or less.

A color resist 1 made from composition (X), a color filter 2 including the color resist 1, and a light emitting device 11 including the color filter 2 will be described.

The color filter 2 includes, for example, a support substrate 4, a color resist 1 supported on the support substrate 4, and a protective layer 5 covering the color resist 1 (see FIGS. 1A and 1B).

The color resist 1 can be produced by molding the composition (X) by an inkjet method and then curing the composition (X) by irradiating it with ultraviolet rays.

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

When the composition (X) has the property of being reduced in viscosity by heating, the composition (X) may be heated and then coated with the composition (X) by an inkjet method and molded. When the viscosity of the composition (X) at 40° C. is 30 mPa·s or less, particularly 15 mPa·s or less, the viscosity can be lowered by slightly heating the composition (X), and this lower viscosity can be lowered by heating the composition (X) slightly. Composition (X) can be discharged by an inkjet method. The heating temperature of composition (X) is, for example, 20°C or more and 50°C or less.

Furthermore, when curing the composition (X), if the phosphor (C) in the composition (X) absorbs ultraviolet rays, the reaction efficiency may decrease due to the phosphor (C) absorbing the ultraviolet rays. It is preferable to select the wavelength of the ultraviolet rays to be irradiated to the composition (X) so that it is unlikely to occur. For example, when a green quantum dot phosphor made of CdSe/ZnS core-shell type semiconductor particles is used, it is preferable that the wavelength of the ultraviolet rays irradiated to the composition (X) is 395 nm or more.

More specifically, for example, first, a transparent support substrate 4 is prepared. The support substrate 4 is made of, for example, transparent resin or glass. A partition wall 3 is fabricated on one surface of this support substrate 4. The partition wall 3 is made of polyimide resin, for example. As a result, a plurality of recesses 14 partitioned by partition walls 3 are formed on the support substrate 4 . Next, composition (X) is discharged into the recess 14 by an inkjet method. Subsequently, the composition (X) in the recess 14 is cured by irradiating it with ultraviolet rays, thereby producing the color resist 1.

Next, a protective layer 5 is formed to cover the color resist 1. The protective layer 5 includes, for example, a layer made of resin (referred to as a resin layer). The protective layer 5 may include a layer made of an inorganic material (referred to as an inorganic layer). The inorganic layer is made of silicon nitride or silicon oxide, for example. The protective layer 5 may include either a resin layer or an inorganic layer, or may include both. When the protective layer 5 includes both a resin layer and an inorganic layer, the protective layer 5 may include a plurality of resin layers or a plurality of inorganic layers. When the protective layer 5 includes a resin layer and an inorganic layer, the adjacent resin layers and inorganic layers in the protective layer 5 are arranged in the direction in which the color resist 1 and the protective layer 5 are arranged. For example, the protective layer 5 may include two inorganic layers and one resin layer, and the inorganic layer, the resin layer, and the inorganic layer may be arranged in this order. The protective layer 5 may include one inorganic layer and two resin layers, and the resin layer, the inorganic layer, and the resin layer may be arranged in this order. The thickness of the protective layer 5 is, for example, 0.1 μm or more and 2 μm or less.

When the protective layer 5 includes an inorganic layer, the inorganic layer can be produced by a vapor deposition method such as a plasma CVD method. In this case, the color resist 1 is exposed to a vacuum or reduced pressure, but as described above, in this embodiment, it is possible to make it difficult for the color resist 1 to generate outgas under a vacuum or reduced pressure. Therefore, even if the color resist 1 is exposed to vacuum or reduced pressure during the manufacturing process of the color filter 2, voids due to outgas are less likely to occur in the color filter 2.

It is preferable that the step of producing color resist 1 from composition (X) does not include a drying step of drying composition (X) after molding it and before curing it. The drying step of drying the composition (X) is to remove at least a portion of the solvent in the composition (X). In this case, since it is not necessary to dry the composition (X), the efficiency of producing the color resist 1 can be increased. In particular, if the composition (X) does not contain a solvent or the content of the solvent is 1% by mass or less, outgassing from the color resist 1 can be suppressed without drying the composition (X).

When composition (X) contains 1% by mass or less of a solvent, the step of producing color resist 1 from composition (X) may include a drying step of drying composition (X), if necessary. In this case, especially if the content of the solvent in composition (X) is 1% by mass or less, the heating temperature and heating time of composition (X) can be reduced when drying composition (X). It is easy to realize at least one of the following. For example, the heating temperature can be 120°C or less, less than 100°C, or less than 50°C. By drying the composition (X), the color resist 1 can be made less likely to generate outgas.

When the method for producing the color filter 2 includes producing the color resist 1 and producing the protective layer 5, this production method includes producing the color resist 1 from the composition (X) and then producing the protective layer 5. It is preferable not to include a drying step of drying the color resist 1 until the color resist 1 is produced. In this case, since it is not necessary to dry the color resist 1, the manufacturing efficiency of the color filter 2 can be improved. Further, in this embodiment, since the composition (X) does not contain a solvent or the content of the solvent is 1% by mass or less, outgas is generated from the color resist 1 even without drying the color resist 1. It can be made difficult.

When the composition (X) contains 1% by mass or less of a solvent, the method for producing the color filter 2 may be changed from the production of the color resist 1 from the composition (X) to the production of the protective layer 5, if necessary. In the meantime, a drying step may be included in which the color resist 1 is dried. In this case, since the content of the solvent in the composition (X) is 1% by mass or less, at least one of the heating temperature and heating time of the color resist 1 can be reduced when drying the color resist 1. is easy to achieve. For example, the heating temperature can be 120°C or less, less than 100°C, or less than 50°C. By drying the color resist 1, outgassing from the color resist 1 can be further suppressed.

The method for producing the color filter 2 includes a drying step of drying the composition (X) and a drying step of drying the color resist 1 between the time when the composition (X) is molded and the time when the protective layer 5 is produced. It is particularly preferable not to include it. However, if the composition (X) contains 1% by mass or less of a solvent, the method for manufacturing the color filter 2 may include a drying step of drying at least one of the composition (X) and the color resist 1, if necessary. May include. Also in this case, as described above, it is easy to achieve at least one of a reduction in heating temperature and a reduction in heating time for drying.

The drying step of drying the composition (X) may include heating the composition (X) under a reduced pressure atmosphere or under vacuum. The drying step of drying the color resist 1 may include heating the color resist 1 under a reduced pressure atmosphere or under vacuum. In these cases as well, the heating temperature can be, for example, 120°C or less, less than 100°C, or less than 50°C.

Note that heating the color resist 1 after producing the color resist 1 for purposes other than drying the color resist 1 is not included in the drying process of drying the color resist 1. For example, heating the color resist 1 in a chamber under vacuum or reduced pressure in order to produce the above-mentioned inorganic layer on the color resist 1 by a vapor deposition method such as a plasma CVD method is not included in the drying process. do not have.

Next, the light emitting device 11 including the color filter 2 will be explained. The light emitting device 11 includes, for example, a color filter 2 including a color resist 1 and a light source that irradiates the color filter 2 with light. The light emitting device 11 may be a display device that visually displays information such as images using light.

The light emitting device 11 shown in FIG. 1A is a display device, more specifically a liquid crystal display device 12. The liquid crystal display device 12 includes a backlight unit 7 including a light source, a liquid crystal panel 6, and a color filter 2, which are stacked in this order. The light source in the backlight unit 7 is, for example, a cold cathode tube or a light emitting diode.

The color resist 1 of the color filter 2 in this liquid crystal display device 12 includes, for example, a color resist 1r that emits red fluorescence (hereinafter also referred to as red color resist 1r) and a color resist 1g that emits green fluorescence (hereinafter referred to as green color resist 1r). 1g) and a resist 1b that does not emit fluorescence (hereinafter also referred to as transparent resist 1b). In this case, if the light source emits blue light, full-color display using the three primary colors is possible. The red color resist 1r and the composition (X) for producing the same contain a quantum dot phosphor (C1) that emits red fluorescence. 1 g of green color resist and the composition (X) for producing the same contain a quantum dot phosphor (C1) that emits green fluorescence. The composition for producing the transparent resist 1b may have a composition obtained by removing the phosphor (C) from the composition (X), as long as it can produce a transparent cured product.

Note that the color of the fluorescence emitted by the color resist 1 in the color filter 2 and the color of the fluorescence emitted by the quantum dot phosphor (C1) are not limited to the above. For example, when the light source emits white light, the color resist 1 may include a color resist that emits blue fluorescence (hereinafter also referred to as blue color resist) instead of the transparent resist 1b. The blue color resist and the composition (X) for producing the same contain a quantum dot phosphor (C1) that emits blue fluorescence. In this case as well, full color display using the three primary colors is possible.

When manufacturing the liquid crystal display device 12, the color filter 2 may be manufactured and then the color filter 2 may be stacked on the liquid crystal panel 6. The color filter 2 may be manufactured by stacking the support substrate 4 on the liquid crystal panel 6 and then manufacturing the partition walls 3, the color resist 1, and the protective layer 5 on the support substrate 4 by the above-described method. The color filter 2 may be produced by directly producing the partition 3, the color resist 1, and the protective layer 5 on the liquid crystal panel 6 by the above-described method.

The liquid crystal display device 12 may further include elements other than those described above. For example, the liquid crystal display device 12 may further include a transparent substrate overlapping the color filter 2. The liquid crystal display device 12 may further include a touch panel that overlaps the color filter 2.

The light emitting device 11 shown in FIG. 1B is a display device, more specifically an LED (light emitting diode) display device. The LED display device 13 includes a light emitting unit 8 including a plurality of light emitting diodes 9 as a light source, and a color filter 2. The light emitting diode 9 is, for example, a micro light emitting diode or an organic light emitting diode (organic electroluminescent device).

The light emitting unit 8 includes a substrate 10, a plurality of light emitting diodes 9 mounted on the substrate 10, and a protective layer 15 covering the light emitting diodes 9. The protective layer 15 in the light emitting unit 8 includes either one of a resin layer and an inorganic layer, or includes both a resin layer and an inorganic layer, like the protective layer 5 in the color filter 2, for example.

The color resist 1 of the color filter 2 in this LED display device 13 includes, for example, a red color resist 1r, a green color resist 1g, and a transparent resist 1b, as in the case of the liquid crystal display device 12 described above. The plurality of color resists 1 in the color filter 2 are paired with each of the plurality of light emitting diodes 9. The light emitted by the light-emitting diode 9 is irradiated onto the color resist 1 serving as a pair, thereby causing the color resist 1 to emit fluorescence. Therefore, when the light emitting diode 9 emits blue light, the light emitted from the LED display device 13 to the outside includes red fluorescence emitted from the red color resist 1r and green fluorescence emitted from the green color resist 1g. This includes blue light that passes through the transparent resist 1b. Therefore, full-color display using the three primary colors is possible.

Note that when the light emitting diode 9 emits white light, a blue color resist that emits blue fluorescence may be included instead of the transparent resist 1b. In this case, the light emitting diode 9 includes a light emitting diode (first light emitting diode) paired with the red color resist 1r, a light emitting diode (second light emitting diode) paired with the green color resist 1g, and a light emitting diode paired with the blue color resist 1g. (a third light emitting diode). In other words, the light emitting diode 9 includes a first light emitting diode that irradiates light onto the red color resist 1r, a second light emitting diode that irradiates light onto the green color resist 1g, and a third light emitting diode that irradiates light onto the blue color resist. It may also include. In this case, the light emitted from the LED display device 13 to the outside includes red fluorescence emitted from the red color resist 1r, green fluorescence emitted from the green color resist 1g, and blue fluorescence emitted from the blue color resist. is included. Therefore, full-color display using the three primary colors is possible.

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

The details of the components shown in the table are as follows. Further, the viscosity of each component below is a value measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 25° C. and a shear rate of 1000 s ^-1 .
-3PG: Tris (propylene glycol) dimethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd., boiling point 400°C, viscosity 13 mPa·s.
-APG200: Tris (propylene glycol) diacrylate, manufactured by Shin Nakamura Chemical Co., Ltd., boiling point 295°C, viscosity 12 mPa·s.
-3G: Triethylene glycol dimethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd., boiling point 290, viscosity 8 mPa·s.
-BD: 1,4-butanediol dimethacrylate, manufactured by Shin Nakamura Chemical Co., Ltd., boiling point 280, viscosity 7 mPa·s.
-SR351S: Trimethylolpropane triacrylate, boiling point 300°C or higher, viscosity 106 mPa·s.
-Bis(4-methacryloylthiophenyl) sulfide: manufactured by Tokyo Kasei Kogyo Co., Ltd., refractive index 1,668, viscosity 20 mPa·s.
- Vinyl phenyl sulfide: manufactured by Tokyo Kasei Kogyo Co., Ltd., refractive index 1.599, viscosity 10 mPa·s.
-VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate, boiling point 260°C, viscosity 4mPa·s.
-ACMO: acryloylmorpholine, boiling point 265, viscosity 12 mPa·s.
-N-vinyl-ε-caprolactam: manufactured by BASF, viscosity 6 mPa・s.
-Irgacure907: manufactured by BASF, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.
-IrgacureTPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide manufactured by BASF.
- Green quantum dot phosphor (C1): CdSe/ZnS core-shell type semiconductor particles, median diameter 3.3 nm, manufactured by SIGMA-ALDRICH, product name CdSe/ZnS530.
- Red quantum dot phosphor (C1): CdSe/ZnS core-shell semiconductor particles, median 5.2 nm, manufactured by SIGMA-ALDRICH, product name: CdSe/ZnS610.
- Hollow acrylic particles 1: Hollow acrylic particles made from an acrylic resin with a refractive index of 1.50, with a median diameter of 400 nm, a hollow ratio of 70%, and a specific gravity of 0.45.
- Hollow acrylic particles 2: Hollow acrylic particles made from acrylic resin with a refractive index of 1.50, with a median diameter of 220 nm, a hollow ratio of 55%, and a specific gravity of 0.55.
- Hollow acrylic particles 3: Hollow acrylic particles made from acrylic resin with a refractive index of 1.50, having a median diameter of 80 nm, a hollowness ratio of 40%, and a specific gravity of 0.75.
- Hollow silica particles: Hollow silica particles made from silica with a refractive index of 1.45, having a median diameter of 60 nm, a hollowness ratio of 44%, and a specific gravity of 1.12.
-Titanium oxide particles: Rutile type titanium dioxide particles, median diameter 210 nm, specific gravity 4.0, manufactured by Huntsman, product number R-TC30.
- Zinc oxide particles: Type 1 zinc oxide, average particle size 0.6 μm, specific gravity 6.2, manufactured by Sakai Chemical.
- Dispersant: a double-terminated and side chain-terminated dispersant having a carboxyl group as an adsorption group, acid value 98 mgKOH/g, viscosity 9000 mP·s, weight average molecular weight 3000, manufactured by Soken Chemical, product number CBB3098.

2. Evaluation Test The following evaluation test was conducted for the Examples and Comparative Examples. The results are shown in the table.

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

(2) Viscosity at 40°C The viscosity of the composition was measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 40°C and a shear rate of 1000 s ^-1 .

(3) Glass transition temperature A composition is applied to create a coating film, and this coating film is heated at 500 mW/cm ² using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus in an air atmosphere. A film with a thickness of 300 μm was produced by photocuring by irradiating ultraviolet light for 20 seconds under the following conditions. The glass transition temperature of a sample cut out from this film was measured using a viscoelasticity measuring device (manufactured by Hitachi High-Tech Science, model number DMA7100).

(4) Adhesion The composition was applied onto a piece of quartz glass (size: 50 mm x 25 mm x 1 mm) to form a coating film with a thickness of 50 μm. Another piece of quartz glass was placed on top of this coating so that the contact area between the two pieces had dimensions of 12.5 mm x 25 mm. Subsequently, the coating film was photocured by irradiating it with ultraviolet light for 20 seconds at 500 mW/cm ² using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus.

Next, the adhesion strength between the two quartz glass pieces was evaluated according to the following criteria by conducting a tensile shear test (tensile speed: 5 mm/min) according to JIS-K-6850.
A: 15MPa or more.
B: Less than 15 MPa.

(5) Outgas evaluation Outgas when the cured product of the composition was heated was sampled using the headspace method and measured using a gas chromatograph. Specifically, 100 mg of the composition was first put into a headspace vial. Subsequently, the composition was irradiated with ultraviolet rays using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus for 3 seconds at a cumulative light intensity of 1500 mJ/cm ² at 500 mW/cm 2 . After curing, the vial was sealed. Subsequently, the composition was heated at 80° C. for 30 minutes, and then the gas phase portion in the vial was introduced into a gas chromatograph and analyzed. As a result, when the gas generated was 300 ppm or less, it was evaluated as "A", when it was more than 300 ppm and less than 500 ppm, it was evaluated as "B", and when it was 500 ppm or more, it was evaluated as "C".

(6) Storage stability The composition was left at a temperature of 40° C. for one month under a nitrogen atmosphere. The viscosity of the composition before this test and the viscosity of the composition after the test were measured using a rheometer (manufactured by Anton Paar Japan, model number DHR-2) at a temperature of 25°C and a shear rate of 1000 s ^-1. The rate of change in viscosity was calculated from the results. The rate of change was evaluated as "A" when it was less than 5%, "B" when it was 5% or more and less than 10%, and "C" when it was 10% or more.

(7) Inkjet property The composition is placed in a cartridge of an inkjet printer (manufactured by Ricoh, model MH2420), and after confirming that the composition in the cartridge can be ejected from the nozzle of the inkjet printer, the composition is ejected from the nozzle. Test patterns were printed continuously. As a result, "A" indicates that the composition could be dispensed for one hour and the dispensing operation was stable, and "B" indicates that the composition could be dispensed for one hour, but the dispensing operation became unstable intermittently. A case where the nozzle became clogged and the composition could no longer be ejected before one hour elapsed from the start of ejection was evaluated as "C".

(8) Refractive index of resin A cured resin was obtained from a mixture containing only a radically polymerizable compound and a photopolymerization initiator among the components of the composition in the same manner as in "(3) Glass transition temperature". . The refractive index of this cured resin product at 25° C. for light with a wavelength of 589 nm was measured using a multiwavelength Abbe refractometer DR-M4 manufactured by Atago.

(9) Wavelength conversion ability The composition was applied onto quartz glass with a thickness of 1 mm, and a coating film of this composition was applied under an atmospheric atmosphere using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus. Then, the film was cured by irradiating ultraviolet rays at 500 mW/cm ² for 3 seconds (integrated light amount 1500 mJ/cm ² ) to produce a film with a thickness of 10 μm. Thereby, a film-attached quartz glass was obtained. The transmittance of this film-attached quartz glass to light at a wavelength of 450 nm was measured. For the measurement, a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) was used. Note that the higher the wavelength conversion ability of the film, the more easily the light with a wavelength of 450 nm is absorbed by the phosphor in the film, and the lower the proportion of the light with a wavelength of 450 nm in the light that passes through the film. Therefore, it can be determined that the lower the measured value of the transmittance of light with a wavelength of 450 nm, the higher the wavelength conversion ability. "A" if the transmittance is 60% or less, "B" if it exceeds 60% but not more than 75%, "C" if it exceeds 75% and not more than 85%, "D" if it exceeds 85%. evaluated.

Claims (17)

It is an ultraviolet curable resin composition used to produce a cured product by molding and then curing,
photopolymerizable compound (A),
photopolymerization initiator (B),
Contains a phosphor (C) and a hollow particle (D),
Contains no solvent or has a solvent content of 1% by mass or less,
The median diameter of the phosphor (C) is 1 nm or more and 10 nm or less,
The median diameter of the hollow particles (D) is 100 nm or more and 3 μm or less,
The hollow particles (D) have a specific gravity of 0.2 or more and 1.2 or less,
The viscosity at 40°C is 5 mPa·s or more and 30 mPa·s or less,
UV curable resin composition. The content ratio of the hollow particles (D) is 0.1% by mass or more and 5% by mass or less,
The ultraviolet curable resin composition according to claim 1. The hollow particles (D) contain hollow resin particles,
The ultraviolet curable resin composition according to claim 1 or 2. The phosphor (C) contains a quantum dot phosphor (C1),
The ultraviolet curable resin composition according to any one of claims 1 to 3. The quantum dot phosphor (C1) contains at least one type of semiconductor particle selected from the group consisting of semiconductor particles that emit red fluorescence, semiconductor particles that emit green fluorescence, and semiconductor particles that emit blue fluorescence. do,
The ultraviolet curable resin composition according to claim 4. The photopolymerizable compound (A) contains a radically polymerizable compound (A1),
The ultraviolet curable resin composition according to any one of claims 1 to 5. The radically polymerizable compound (A1) contains a compound having nitrogen in its molecular skeleton,
The ultraviolet curable resin composition according to claim 6. The radically polymerizable compound (A1) contains an acrylic compound (Y),
The ultraviolet curable resin composition according to claim 6 or 7. The acrylic compound (Y) contains a polyfunctional acrylic compound (Y1),
The ultraviolet curable resin composition according to claim 8. The photopolymerization initiator (B) contains a photopolymerization initiator having photobleaching properties,
The ultraviolet curable resin composition according to any one of claims 1 to 9. Molded using the inkjet method,
The ultraviolet curable resin composition according to any one of claims 1 to 10. For making color resist,
The ultraviolet curable resin composition according to any one of claims 1 to 11. comprising a cured product of the ultraviolet curable resin composition according to any one of claims 1 to 12,
Color resist. comprising a color resist according to claim 13;
color filter. comprising the color filter according to claim 14 and a light source that irradiates light to the color filter,
Light emitting device. is a display device,
The light emitting device according to claim 15. After molding the ultraviolet curable resin composition according to any one of claims 1 to 12 by an inkjet method, the ultraviolet curable resin composition is cured by irradiating ultraviolet rays.
Method of manufacturing color resist.

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