WO2022080359A1

WO2022080359A1 - Wavelength conversion member molding composition, color resist, color filter, method for manufacturing color resist, light emitting device, and method for manufacturing light emitting device

Info

Publication number: WO2022080359A1
Application number: PCT/JP2021/037703
Authority: WO
Inventors: 考弘千秋; 祐輔浦岡; 裕基池上
Original assignee: パナソニックＩｐマネジメント株式会社
Priority date: 2020-10-12
Filing date: 2021-10-12
Publication date: 2022-04-21
Also published as: JPWO2022080359A1

Abstract

The present invention addresses the problem of providing a wavelength conversion member molding composition that is used to produce a wavelength conversion member, is capable of increasing the wavelength conversion efficiency of light when the wavelength conversion member is irradiated with the light, and does not tend to impair preservation stability. This wavelength conversion member molding composition contains a reaction curable compound (A), a phosphor (B), and light scattering particles (C). The light scattering particles (C) include a core-shell particle (C0) having a core part and a shell covering the core part. The specific gravity of the core part is 2.0 or less. The refractive index of the shell is 1.9 or more.

Description

A composition for forming a wavelength conversion member, a color resist, a color filter, a method for manufacturing a color resist, a light emitting device, and a method for manufacturing a light emitting device.

The present disclosure relates to a composition for forming a wavelength conversion member, a color resist, a color filter, a method for manufacturing a color resist, a light emitting device, and a method for manufacturing a light emitting device. , A color resist produced from this wavelength conversion member molding composition, a color filter including this color resist, a method for manufacturing this color resist, a light emitting device equipped with this color filter, and light emission using the wavelength conversion member molding composition. Regarding the manufacturing method of the device.

Patent Document 1 describes an ink composition for forming a light conversion layer used in an inkjet method, which comprises luminescent nanocrystal particles, light scattering particles, a photopolymerizable compound and / or a thermosetting resin. It is disclosed that the contained and light-scattering particles contain titanium oxide and the like. As a result, the light is scattered by the light-scattering particles, thereby increasing the wavelength conversion efficiency of the luminescent nanocrystal particles.

International Publication No. 2018/123103

In manufacturing a wavelength conversion member such as a color filter, the inventor blends light-scattering particles in a molding material as in Patent Document 1 to scatter light in the wavelength conversion member for wavelength conversion efficiency. I was conducting research to increase the number of light.

However, according to the inventor's own research, if particles having a high refractive index such as titanium oxide particles as in the case of Patent Document 1 are used as the light scattering particles, high light scattering properties can be obtained, but the composition. Particles tend to settle inside, which impairs the storage stability of the composition.

The subject of the present disclosure is a wavelength that can be used for manufacturing a wavelength conversion member, can increase the wavelength conversion efficiency of light when the wavelength conversion member is irradiated with light, and does not easily impair storage stability. A composition for forming a conversion member, a color resist produced from the composition for forming a wavelength conversion member, a color filter including the color resist, a method for manufacturing the color resist, a light emitting device equipped with the color filter, and molding of the wavelength conversion member. It is an object of the present invention to provide a method of manufacturing a light emitting device using a composition for use.

The composition for forming a wavelength conversion member according to the first aspect of the present disclosure contains a reaction-curable compound (A), a phosphor (B) and light-scattering particles (C). The light-scattering particle (C) includes a core-shell type particle (C0) having a core portion and a shell covering the core portion. The specific gravity of the core portion is 2.0 or less. The refractive index of the shell is 1.9 or more.

The composition for forming a wavelength conversion member according to the second aspect of the present disclosure contains a reaction-curable compound (A), a phosphor (B) and light-scattering particles (C). The light scattering particles (C) contain titanium oxide particles (C1) and hollow particles (C2).

The color resist according to the present disclosure includes a cured product of the composition for forming a wavelength conversion member according to the first or second aspect.

The color filter according to the present disclosure includes the color resist.

In the method for producing a color resist according to one aspect of the present disclosure, the wavelength conversion member molding composition is molded by an inkjet method, and then the wavelength conversion member molding composition is irradiated with ultraviolet rays to be cured.

The light emitting device according to the present disclosure includes the color filter and a light source that irradiates the color filter with light.

The method for manufacturing a light emitting device according to one aspect of the present disclosure is a method for manufacturing a light emitting device including a color filter including a color resist and a light source for irradiating the color filter with light. Manufactured by the method of manufacturing color resist.

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

Hereinafter, preferred embodiments of the present disclosure will be described.

The composition for forming a wavelength conversion member according to the present embodiment (hereinafter, also referred to as composition (X)) contains a reaction-curable compound (A), a fluorescent substance (B), and light-scattering particles (C).

In the first embodiment, the light scattering particle (C) includes a core shell type particle (C0) having a core portion and a shell covering the core portion. The specific gravity of the core portion is 2.0 or less. The refractive index of the shell is 1.9 or more.

The refractive index is the refractive index for the sodium D line (wavelength 589.3 nm) at 25 ° C.

In the second embodiment, the light scattering particles (C) contain titanium oxide particles (C1) and hollow particles (C2).

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

In the present embodiment, when the wavelength conversion member is irradiated with light, the light scattering particles (C) can scatter the light in the cured product. Therefore, there are many opportunities for light to reach the phosphor (B) in the cured product, and as a result, the efficiency of wavelength conversion is increased. Therefore, the wavelength conversion member can exhibit high wavelength conversion efficiency in comparison with its size.

In the second embodiment, since the titanium oxide particles (C1) in particular have high light scattering properties in the resin, the chances of light reaching the phosphor (B) in the cured product increase, and the efficiency of wavelength conversion is increased. It is effective in increasing.

Further, in the second embodiment, although the composition (X) contains titanium oxide particles (C1) having a relatively high specific gravity, the light scattering particles (C) are generated during storage of the composition (X). It is difficult to settle, that is, the titanium oxide particles (C1) do not easily impair the storage stability of the composition (X). This is because the light-scattering particles (C) contain the hollow particles (C2) together with the titanium oxide particles (C1), and the interaction between the two causes the precipitation of not only the hollow particles (C2) but also the titanium oxide particles (C1). It is presumed that this is because it becomes difficult to do.

In a preferred embodiment of the present disclosure, when the wavelength conversion member is produced using the composition (X), it is preferably molded by an inkjet method. In this case, the wavelength conversion member can be manufactured with high position accuracy. Further, for this reason, the wavelength conversion member can be made high-definition, that is, a minute wavelength conversion member can be manufactured at a high density. Therefore, for example, it is possible to realize high definition (high resolution) of the light emitting device 11 provided with the color filter 2, particularly the display device. Further, when the composition (X) is molded by the inkjet method, foreign matter is less likely to be mixed into the composition (X) and its cured product as compared with the case of molding by a printing method involving contact such as a screen printing method. Therefore, the yield in manufacturing the wavelength conversion member is unlikely to deteriorate. The composition (X) may be molded by a method other than the inkjet method such as a screen printing method.

When the composition (X) is molded by the inkjet method, it is difficult to increase the thickness dimension of the wavelength conversion member produced from the composition (X), so that the thickness of the wavelength conversion member is, for example, 10 μm or less. However, in the present embodiment, as described above, the wavelength conversion member can exhibit high wavelength conversion efficiency in comparison with its size, so that high wavelength conversion efficiency can be exhibited even if the thickness of the wavelength conversion member is small.

It is preferable that the composition (X) does not contain a solvent, or the content of the solvent (percentage of the solvent to the whole composition (X)) is 1% by mass or less. In this case, outgas derived from the solvent is unlikely to be generated from the composition (X) and the cured product of the composition (X). Therefore, the change in viscosity of the composition (X) due to the volatilization of the solvent is less likely to occur, which enhances the storage stability of the composition (X). Further, it is possible to prevent the formation of voids due to outgas in the wavelength conversion member. Therefore, it is difficult for water to reach the wavelength conversion member through the void, and the phosphor (B) in the wavelength conversion member is less likely to be deteriorated by water. Further, the drying step for removing the solvent from the composition (X) and the cured product at the time of producing the wavelength conversion member can be eliminated. 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 reduction of the heating temperature and shortening of the heating time in the drying step is possible. Can be done. Therefore, outgas can be less likely to be generated from the wavelength conversion member without lowering the manufacturing efficiency of the wavelength conversion member. Further, if the composition (X) does not contain a solvent, or if the content of the solvent is 1% by mass or less, the composition (X) after molding is formed, especially when the composition (X) is molded by an inkjet method. ), The thickness is less likely to decrease due to the volatilization of the solvent, and therefore the thickness of the wavelength conversion member is less likely to decrease. Therefore, the thickness of the wavelength conversion member can be secured as large as possible while molding by the inkjet method, and the wavelength conversion ability of the wavelength conversion member can be secured as large as possible. The content of the solvent is more preferably 0.5% by mass or less, further preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. It is particularly preferable that the composition (X) does not contain a solvent or contains only a solvent that is inevitably mixed. The solvent content of the composition (X) may exceed 1% by mass.

The glass transition temperature of the cured product of the composition (X) is preferably 80 ° C. or higher. That is, it is preferable that the composition (X) has a property of becoming a cured product having a glass transition temperature of 80 ° C. or higher when cured. In this case, the wavelength conversion member can have good heat resistance. Therefore, for example, when the wavelength conversion member is subjected to a process accompanied by a temperature rise, the wavelength conversion member is less likely to deteriorate. Therefore, for example, when the protective layer is manufactured by a vapor deposition method such as a plasma CVD method so as to cover the wavelength conversion member manufactured from the composition (X), the wavelength conversion member is less likely to deteriorate even if the wavelength conversion member is heated. .. Further, by increasing the heat resistance, the wavelength conversion member can be adapted to in-vehicle applications where the demand for heat resistance is strict. The glass transition temperature of the cured product is more preferably 90 ° C. or higher, and even more preferably 100 ° C. or higher. The glass transition temperature of this cured product can be achieved by the composition of the composition (X) described in detail below.

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

It is also preferable that the viscosity of the composition (X) at 40 ° C. is 30 mPa · s or less. In this case, regardless of the viscosity of the composition (X) at room temperature, the viscosity can be reduced by slightly heating the composition (X). Therefore, if heated, the composition (X) can be molded by an inkjet method. Further, since the composition (X) can be reduced in viscosity without being significantly heated, it is possible to prevent the composition (X) from changing due to volatilization of the components in the composition (X). If the viscosity is 25 mPa · s or less, it is more preferable, if it is 20 mPa · s or less, it is further preferable, and if it is 15 mPa · s or less, it is particularly preferable. It is preferable that the viscosity is 1 mPa · s or more, and it is also preferable that the viscosity is 5 mPs or more.

The low viscosity of such composition (X) at 25 ° C. or 40 ° C. can be achieved by the composition of composition (X) described in detail below.

The volatility when 20 mg of the composition (X) is heated using a thermogravimetric analyzer under the condition of 100 ° C. for 30 minutes is preferably 40% or less. The volatility of the composition (X) is the weight loss of the composition (X) after the treatment with respect to the weight of the composition (X) before the treatment (the weight of the composition (X) before the treatment and the weight after the treatment). It is defined as a percentage of the difference from the weight). In this case, the low volatility of the composition (X) can enhance the storage stability of the composition (X). In addition, outgas is less likely to be generated from the wavelength conversion member. Therefore, voids due to outgas are less likely to occur in the wavelength conversion member. The volatility of the composition (X) is determined by heating 20 mg of the composition (X) using a thermogravimetric analyzer under the condition of 100 ° C. for 30 minutes, and the weight loss after the treatment with respect to the weight before the treatment. Can be obtained by calculating. The volatility when 20 mg of the composition (X) is heated using a thermogravimetric analyzer at 100 ° C. for 30 minutes is more preferably 30% or less, and further preferably 20% or less. preferable. The lower limit of the volatility of the composition (X) is not particularly limited, but may be, for example, 0.1% or more.

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

<Reaction-curable compound (A)>
First, the reaction-curable compound (A) will be described. The reaction-curable compound (A) contains, for example, at least one of a photocurable compound (A1) and a thermosetting compound (A2).

The photocurable compound (A1) is a component capable of causing a polymerization reaction by being irradiated with ultraviolet rays in the presence or absence of, for example, a photopolymerization initiator (E). The photopolymerization initiator (E) may contain a curing catalyst. The photocurable compound (A1) contains at least one component selected from the group consisting of, for example, monomers, oligomers and prepolymers.

The photocurable compound (A1) contains, for example, at least one of a radically polymerizable compound (A11) and a cationically polymerizable compound (A12). When the photocurable compound (A1) contains a radically polymerizable compound (A11), the composition (X) preferably further contains a photoradical polymerization initiator (E1) as a photopolymerization initiator (E). .. When the photocurable compound (A1) contains a cationically polymerizable compound (A12), the composition (X) contains a photocationic polymerization initiator (E2) (cationic curing catalyst) as the photopolymerization initiator (E). Further, it is preferable to contain it.

Further, the thermosetting compound (A2) has at least one reactive functional group consisting of, for example, an epoxy group, an oxetane group, an isocyanate group, an amino group, a carboxyl group, a methylol group and the like. The thermosetting compound (A2) contains at least one component selected from the group consisting of, for example, monomers, oligomers and prepolymers.

The viscosity of the entire reaction-curable compound (A) at 25 ° C. is preferably 50 mPa · s or less. In this case, the reaction-curable compound (A) can make the composition (X) particularly low in viscosity. The viscosity of the entire reaction-curable compound (A) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. Further, the viscosity of the entire reaction-curable compound (A) is, for example, 3 mPa · s or more.

It is also preferable that the viscosity of the entire reaction-curable compound (A) at 40 ° C. is 50 mPa · s or less. In this case, the reaction-curable compound (A) can make the composition (X) particularly low in viscosity when heated. The viscosity of the entire reaction-curable compound (A) is more preferably 30 mPa · s or less, and particularly preferably 20 mPa · s or less. The viscosity of the entire reaction-curable compound (A) is, for example, 3 mPa · s or more.

The percentage of the component having a boiling point of 270 ° C. or higher in the reaction-curable compound (A) is preferably 80% by mass or more. In this case, the storage stability of the composition (X) is particularly unlikely to be impaired, and outgas is particularly unlikely to be generated from the cured product. It is more preferable that the percentage of the component having a boiling point of 280 ° C. or higher in the reaction-curable compound (A) is 80% by mass or more.

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

The ratio of the component having a viscosity of 20 mPa · s or less at 25 ° C. to the total amount of the reaction-curable compound (A) is preferably 50% by mass or more and 100% by mass or less. In this case, the composition (X) can be made particularly low in viscosity, and the composition (X) can be applied particularly easily by an inkjet method. This ratio is more preferably 60% by mass or more, and further preferably 70% by mass or more. Further, this ratio is more preferably 95% by mass or less, and further preferably 90% by mass or less.

The component having a viscosity at 25 ° C. of 20 mPa · s or less 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 if it contains a compound having a glass transition temperature of 100 ° C. or higher. The upper limit of the glass transition temperature of the compound contained in this component is not limited, but is, for example, 150 ° C. or lower.

The reaction-curable compound (A) preferably contains a photocurable compound (A1). In this case, since it is not necessary to heat the composition (X) in order to cure it, the light source or the like in the light emitting device 11 can be less likely to be damaged by heat, particularly when the color resist 1 in the light emitting device 11 is manufactured as a wavelength conversion member. ..

When the photocurable compound (A1) contains a radically polymerizable compound (A11), the radically polymerizable compound (A11) preferably contains an acrylic compound (Y). The acrylic compound (Y) has one or more (meth) acryloyl groups in one molecule.

The compound that the acrylic compound (Y) can contain will be described.

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 thus can increase the heat resistance of the cured product. The ratio of the polyfunctional acrylic compound (Y1) is preferably 50% by mass or more and 100% by mass or less with respect to the entire acrylic compound (Y). The 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 oligo acrylate, diethylene glycol diacrylate, 1,6-hexanediol oligo acrylate, neopentyl glycol diacrylate, Triethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, pentaerythritol tetraacrylate , Propoxylation (2) Neopentyl glycol diacrylate, Trimethylol propantriacrylate, Tris (2-hydroxyethyl) isocyanurate triacrylate, Pentaerythritol triacrylate, ethoxylated (3) Trimethylol propoxytriacrylate, Propoxylation (3) ) Glyceryltriacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, 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-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate , 1,4-Butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol hydroxypivalate Diacrylate, hydroxypivalic acid trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylol propanediacrylate, stearate-modified pentaerythritol diacrylate, tetramethylol propanetriac Relate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, propoxylate glyceryl triacrylate, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, di Pentaerythritol hydroxypentaacrylate, neopentyl glycol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol di ( It contains at least one compound selected from the group consisting of meth) acrylates, ethoxylated trimethylolpropane triacrylates, propoxylated trimethylolpropane triacrylates, and 2- (2-vinyloxyethoxy) ethyl acrylate.

The acrylic equivalent of the polyfunctional acrylic compound (Y1) is preferably 150 g / eq or less, and 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 represented by 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 a hydrogen or 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, it is in one molecule. The plurality of ^R3s may be the same as or different from each other.

Since the compound (Y11) has the structure represented by the formula (200), and particularly the carbon number of R3 of the formula (200) is ³ or more, it is difficult to increase the affinity of the cured product with water. Therefore, the phosphor (B) is less likely to be deteriorated by water. The carbon number of R ³ is, for example, 1 or more and 15 or less, preferably 3 or more and 15 or less. Further, the compound (Y11) has a structure represented by the formula (200), and in particular, by having two (meth) acryloyl groups in one molecule, the glass transition temperature of the cured product can be increased, and therefore the glass transition temperature can be increased. , The heat resistance of the cured product can be improved. Further, n in the equation (200) is, for example, an integer of 1 or more and 12 or less.

The percentage of the compound (Y11) to the acrylic compound (Y) is preferably 50% by mass or more. In this case, it is difficult to increase the affinity of the cured product for water. The percentage 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 compound (Y11) preferably contains a component having a boiling point of 270 ° C. or higher. That is, the acrylic compound (Y) preferably contains a component having a structure represented by the formula (200) and having a boiling point of 270 ° C. or higher. In this case, the acrylic compound (Y) is less likely to volatilize from the composition (X) during storage of the composition (X) and when the composition (X) is heated. Therefore, the storage stability of the composition (X) is not easily impaired. Further, even if the compound (Y11) remains unreacted in the cured product of the composition (X), outgas caused by the compound (Y11) is unlikely to be generated from the cured product. Therefore, voids due to outgas are unlikely to occur in the color filter 2. If there are voids in the color filter 2, water may invade the color resist 1 through the voids, but if the voids are less likely to occur, it is difficult for water to invade the color resist 1. The boiling point is the boiling point under normal pressure obtained by converting the boiling point under reduced pressure, and is obtained by, for example, the method shown in Science of Petroleum, Vol.II. P.1281 (1938). It is more preferable that the compound (Y11) contains a component having a boiling point of 280 ° C. or higher.

The percentage of the compound (Y11) to the acrylic compound (Y) is preferably 50% by mass or more. In this case, the storage stability of the composition (X) is effectively enhanced, the outgas generation from the cured product is effectively reduced, and the affinity of the cured product with water is particularly difficult to be enhanced. The percentage 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, the compound (Y11) can reduce the viscosity of the composition (X). The viscosity of the compound (Y11) at 25 ° C. is more preferably 25 mPa · s or less, further preferably 20 mPa · s or less, and particularly preferably 15 mPa · s or less. The viscosity of the compound (Y11) at 25 ° C. is, for example, 1 mPa · s or more, preferably 3 mPa · s or more, and even more preferably 5 mPa · s or more.

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

The alkylene glycol di (meth) acrylate is a compound in which n is 1 in the formula (200). In this case ^, the carbon number of R3 in the formula (200) is preferably 4 to 12. ^R3 may be linear or may have a branch. In particular, the alkylene glycol di (meth) acrylate is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol di. Acrylic, 1,10-decanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol It preferably contains at least one compound selected from the group consisting of dimethacrylate, 1,10-decanediol dimethacrylate and 1,12-dodecanediol dimethacrylate. In addition, the alkylene glycol di (meth) acrylate has a product number SR213 manufactured by Sartmer, a product number V195 manufactured by Osaka Organic Chemical Industry Co., Ltd., a product number SR212 manufactured by Sartmer Co., Ltd., a product number SR247 manufactured by Sartmer Co., Ltd., and a product name light manufactured by Kyoei Chemical Industry Co., Ltd. Acrylate NP-A, product number SR238NS manufactured by Sartmer, product number V230 manufactured by Osaka Organic Chemical Industry Co., Ltd., product number HDDA manufactured by Daicel Co., Ltd., product number 1,6HX-A manufactured by Kyoei Chemical Industry Co., Ltd., product number manufactured by Osaka Organic Chemical Industry Co., Ltd. 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 Sartmer Co., Ltd., product number SR214NS manufactured by Sartmer Co., Ltd. Product number BD, product number SR297 manufactured by Sartmer, product number SR248 manufactured by Sartmer, product name Light Ester NP manufactured by Kyoei Chemical Industry Co., Ltd., product number SR239NS manufactured by Sartmer Co., Ltd., 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 the product number DOD-N manufactured by Shin-Nakamura Chemical Industry Co., Ltd. and the product number SR262 manufactured by Sartmer Co., Ltd.

The polyalkylene glycol di (meth) acrylate is, for example, a compound in which n is 2 or more in the formula (200). n is, for example, 2 to 10, preferably 2 to 7, preferably 2 to 6, and preferably 2 to 3. The carbon number of R3 is ^, for example, 2 to 7, preferably 2 to 5. The higher the number of carbon atoms, the higher the hydrophobicity of the cured product, and the more difficult it is for the cured product to permeate moisture. Polyalkylene glycol di (meth) acrylates include, in particular, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and tri. It preferably contains at least one compound selected from the group consisting of propylene glycol dimethacrylate, tritetramethylene glycol diacrylate, polyethylene glycol 200 dimethacrylate and polyethylene glycol 200 diacrylate. Further, the polyalkylene glycol di (meth) acrylate is particularly the product number SR230 manufactured by Sartmer, the product number SR508NS manufactured by Sartmer, the product number DPGDA manufactured by Dycel, the product number SR306NS manufactured by Sartmer, the product number TPGDA manufactured by Dysel, and Osaka Organic. Product number V310HP manufactured by Chemical Industry 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 Sartmer Co., Ltd., Product name Light Ester 2EG manufactured by Kyoei Chemical Industry Co., Ltd. Product number SR205NS manufactured by Sartmer, product name Light Ester 3EG manufactured by Kyoei Chemical Industry Co., Ltd., product name SR210NS manufactured by Sartmer Co., Ltd., product name Light Ester 4EG manufactured by Kyoei Chemical Industry Co., Ltd. It is preferable to contain at least one compound selected from the group consisting of product number 3PG manufactured by the company.

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 contains, for example, product number EBECRYL145 manufactured by Daicel Corporation.

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

It is particularly preferable if the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di (meth) acrylate. Since the polyalkylene glycol di (meth) acrylate has a low viscosity and is hard to volatilize, it can contribute to lowering the viscosity of the composition (X), and the storage stability of the composition (X) is improved and the cured product is used. It can contribute to the reduction of outgas.

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

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

The polyfunctional acrylic compound (Y1) preferably contains pentaerythritol tetra (meth) acrylate. In this case, the glass transition temperature of the cured product can be particularly increased, and the reactivity of the composition (X) can be improved. When the reactivity of the composition (X) is improved, the composition (X) can be easily cured 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) shall be 0.5% by mass or more and 10% by mass or less. Is preferable. In this case, it is possible to achieve both high reactivity and low viscosity of the composition (X). This ratio is more preferably 1% by mass or more and 9% by mass or less, and further 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 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. Further, it is possible to enhance the adhesion between the cured product and an inorganic compound such as silicon nitride or silicon oxide. The polyfunctional acrylic compound (Y1) is particularly selected from the group consisting of tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate, bisphenol F polyethoxydiacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate. It preferably contains one type of compound. These compounds can particularly reduce shrinkage as the composition (X) cures. Furthermore, these compounds can also enhance the adhesion between the cured product and inorganic compounds such as silicon nitride and silicon oxide.

When the adhesion between the cured product and the inorganic material is increased, when the color resist 1 is overlapped with a film (inorganic film) made of an inorganic material such as a SiN film, the adhesion between the color resist 1 and the inorganic film is high. Can be obtained. Strictly speaking, the adhesion between the cured resin matrix of the photocurable compound (A1) and the inorganic compound is enhanced, so that the phosphor (B) is an inorganic particle such as a quantum dot phosphor (B1). In the cured product, the adhesion between the resin matrix and the phosphor (B) can be enhanced.

It is particularly preferable that the polyfunctional acrylic compound (Y1) contains a polyalkylene glycol di (meth) acrylate and a pentaerythritol tetra (meth) acrylate. In this case, the composition (X) has a low viscosity and is excellent in 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 of the composition (X) during curing.

The amount of the monofunctional acrylic compound (Y2) with respect to the total amount of the acrylic compound (Y) is preferably more than 0% by mass and 50% by mass or less. When the amount of the monofunctional acrylic compound (Y2) is more than 0% by mass, the shrinkage of the composition (X) at the time of curing can be suppressed. Further, when the amount of the monofunctional acrylic compound (Y2) is 50% by mass or less, the amount of the polyfunctional acrylic compound (Y1) can be 50% by mass or more, so that the heat resistance of the cured product can be particularly improved. It is more preferable that the amount of the monofunctional acrylic compound (Y2) is 5% by mass or more, and further preferably 30% by mass or less.

The monofunctional acrylic compound (Y2) is, for example, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate. , Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydixyl ethyl acrylate, ethyl diglycol acrylate, cyclic trimethyl propaneformal monoacrylate, Iimide acrylate, isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, cyclohexyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, Isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nonylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene Glycol (550) monoacrylate, phenoxyethyl acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, Caprolactone-modified tetrahydrofurfuryl acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, ethylene oxide adduct of 2-phenoxyethyl acrylate, propylene oxide adduct of 2-phenoxyethyl acrylate, acryloylmorpholine, Morpholine-4-yl acrylate, dicyclopentanyl acrylate, phenoxydiethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate Contains at least one compound selected from the group consisting of 1,4-cyclohexanedimethanol monoacrylate, 3-methacryloyloxymethylcyclohexene oxide and 3-acryloyloxymethylcyclohexene oxide.

The monofunctional acrylic compound (Y2) may contain at least one compound selected from the group consisting of 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 acryloylmorpholin, 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.

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

The acrylic compound (Y) may contain a compound having silicon in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having silicon in the molecular skeleton include, for example, 3- (trimethoxysilyl) propyl acrylate (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.). It 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 the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. Compounds having phosphorus in the molecular skeleton include acid phosphoxy (meth) acrylates such as acid phosphooxypolyoxypropylene glycol monomethacrylate.

The acrylic compound (Y) may contain a compound having nitrogen in the molecular skeleton. In this case, the adhesion between the cured product and the inorganic material is improved. In addition, the reactivity of the acrylic compound (Y) is improved, so that outgas is less likely to be generated from the cured product. The compound having nitrogen in the molecular skeleton is selected from the group consisting of compounds having a morpholine skeleton such as acryloyl morpholine and morpholine-4-yl acrylate, diethylacrylamide, dimethylaminopropylacrylamide and pentamethylpiperidylmethacrylate. 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 air atmosphere can be further improved. It is particularly preferable that the acrylic compound (Y) contains at least one of acryloyl morpholine and morpholine-4-yl acrylate. In this case, shrinkage of the composition (X) during curing can be suppressed. In addition, the viscosities of acryloyl morpholine and morpholine-4-yl acrylate are low, so that these compounds do not easily increase the viscosity of the composition (X). Furthermore, since these compounds are less likely to volatilize, the storage stability of the composition (X) can be 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 the composition (X). This ratio is more preferably 7% by mass or more and 45% by mass or less, and further 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, for example, tricyclodecanedimethanol diacrylate, bisphenol A polyethoxydiacrylate and bisphenol F polyethoxydiacrylate. good. In this case, the adhesion between the cured product and the inorganic material can be improved.

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

In formula (100), ^R0 is an H or a methyl group. X is a single bond or 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 (A11) may contain a radically polymerizable compound (Z) other than the acrylic compound (Y). The amount of the radically polymerizable compound (Z) with respect to the total amount of the acrylic compound (Y) and the radically polymerizable compound (Z) is, for example, 10% by mass or less. The radically polymerizable compound (Z) is a polyfunctional radically polymerizable compound (Z1) having two or more radically polymerizable functional groups in one molecule, and a monofunctional compound having only one radically polymerizable functional group in one molecule. One or both of the radically polymerizable compound (Z2) can be contained. The polyfunctional radically polymerizable compound (Z1) is, for example, a group consisting of aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers and other special oligomers having two or more ethylenic double bonds in one molecule. It may contain at least one compound selected from. The components that can be contained in the polyfunctional radically polymerizable compound (Z1) are not limited to the above. The monofunctional radically polymerizable compound (Z2) includes, for example, N-vinylformamide, vinylcaprolactum, vinylpyrrolidone, phenylglycidyl ether, p-tert-butylphenylglycidyl ether, butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, and the like. 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene It contains at least one compound selected from the group consisting of oxide, N-vinylpyrrolidone and N-vinylcaprolactam. The components that can be contained in the monofunctional radically polymerizable compound (Z2) are not limited to the above.

When the radically polymerizable compound (A11) contains the radically polymerizable compound (Z), the radically polymerizable compound (Z) may contain a compound having nitrogen in the molecular skeleton. Compounds having nitrogen in the molecular skeleton include, for example, at least one compound selected from the group consisting of N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. In this case, the adhesion between the cured product and the inorganic material is improved as in the case where the acrylic compound (Y) contains a compound having nitrogen in the molecular skeleton.

In other words, the radically polymerizable compound (A11) preferably contains a compound having nitrogen in the molecular skeleton. The compound having nitrogen in the molecular skeleton may contain the compound contained in the acrylic compound (Y) or may contain the compound contained in the radically polymerizable compound (Z). In this case, the adhesion between the cured product and the inorganic material is improved. The ratio of the compound having nitrogen in the molecular skeleton to the whole radically polymerizable compound (A11) is preferably 5% by mass or more and 80% by mass or less. When this ratio is 5% by mass or more, the adhesion between the cured product and the inorganic material can be particularly improved. When this ratio is 80% by mass or less, the compound having nitrogen in the molecular skeleton does not easily impair the storage stability of the composition (X), and the satellite when the composition (X) is jetted by the inkjet method can be used. Hard to cause. Therefore, the inkjet property of the composition (X) is less likely to be impaired. Further, it is possible to reduce the generation of outgas caused by the compound having nitrogen in the molecular skeleton. This ratio is more preferably 10% by mass or more and 70% by mass or less, further preferably 20% by mass or more and 60% by mass or less, and particularly preferably 25% by mass or more and 50% by mass or less.

The photoradical polymerization initiator (E1) is not particularly limited as long as it is a compound that produces radical species when irradiated with ultraviolet rays. The photoradical polymerization initiator (E1) is, for example, aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole. It contains at least one compound selected from the group consisting of a 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 (E1) with respect to 100 parts by mass of the composition (X) is, for example, 1 part by mass or more and 10 parts by mass or less.

The photoradical polymerization initiator (E1) preferably contains an initiator having photobleaching properties. In this case, the light transmittance of the cured product can be increased.

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

The oxime ester compound having photobleaching property contains, for example, at least one of the compound represented by the following formula (401) and the compound represented by the following formula (402). Of these, the compound represented by the formula (402) has particularly high sensitivity, so that the photocurability of the composition (X) can be particularly enhanced.

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

The photoradical polymerization initiator (E1) may contain a sensitizer as a part of the photoradical polymerization initiator (E1). The sensitizer can accelerate the radical generation reaction of the photoradical polymerization initiator (E1), improve the reactivity of the radical polymerization, and improve the crosslink density. The sensitizer is, for example, 9,10-dibutoxyanthracene, 9-hydroxymethylanthracene, thioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, anthracinone, 1,2-. Dihydroxyanthracene, 2-ethylanthracene, 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. The components that the sensitizer can contain are not limited to the above.

The content of the sensitizer in the composition (X) is, for example, 0.1 part by mass or more and 5 parts by mass or less, preferably 0.1 part by mass, with respect to 100 parts by mass of the solid content of the composition (X). It is 3 parts or more and 3 parts by mass or less. When the content of the sensitizer is in such a range, the composition (X) can be cured in air, and the composition (X) needs to be cured in an inert atmosphere such as a nitrogen atmosphere. It disappears.

The composition (X) may contain a polymerization accelerator in addition to the photoradical polymerization initiator (E1). Examples of the polymerization accelerator include ethyl p-dimethylaminobenzoate, -2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, -2-dimethylaminoethyl benzoate, and butoxy p-dimethylaminobenzoate. Contains amine compounds such as ethyl. The components that can be contained in the polymerization accelerator are not limited to the above.

When the photocurable compound (A1) contains the cationically polymerizable compound (A12), the cationically polymerizable compound (A12) may be, for example, a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). Contains at least one of them.

The polyfunctional cationically polymerizable compound (W1) is either one or both of a polyfunctional cationically polymerizable compound (W11) having no siloxane skeleton and a polyfunctional cationically polymerizable compound (W12) having a siloxane skeleton. Can be contained.

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

The polyfunctional cationically polymerizable compound (W11) is composed of, for example, a polyfunctional alicyclic epoxy compound, a polyfunctional heterocyclic epoxy compound, a polyfunctional oxetane compound, an alkylene glycol diglycidyl ether, and an alkylene glycol monovinyl monoglycidyl ether. It contains at least one compound among the selected compounds.

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

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

In the formula (1), X is a single bond or a divalent organic group, and the organic group is, for example, -CO-O-CH2-.

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. The hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group; or an ethylidene group and propyridene. 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 preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms independently, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

Examples of the compound represented by the formula (20) include a tetrahydroinden epoxide represented by the following formula (20a).

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 the compounds represented by the following formulas (4) to (7).

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

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

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

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

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

Further, since the compound represented by the formula (20) has a low viscosity, the composition (X) can have good ultraviolet curability and particularly when the compound represented by the formula (20) is contained. It can have a low viscosity. Further, the compound represented by the formula (20) has a property of being hard to volatilize in spite of having a low viscosity. Therefore, even if the composition (X) contains the compound represented by the formula (20), the composition (X) is unlikely to change in composition due to the volatilization of the compound represented by the formula (20). Therefore, the composition (X) can be reduced in viscosity by containing the compound represented by the formula (20) without impairing the storage stability.

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

The compound represented by the formula (20) may contain four stereoisomers based on the configuration of the two epoxy rings. The compound represented by the formula (20) may contain any of the four stereoisomers. That is, the compound represented by the formula (20) can contain at least one component selected from the group consisting of four stereoisomers. The ratio of the total amount of the exo-end form and the end-end form to the four stereoisomers in the compound represented by the formula (20) is 10% by mass or less with respect to 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. The ratio of the specific stereoisomer in the compound represented by the formula (20) can be determined based on the peak area ratio appearing in the chromatogram obtained by gas chromatography.

In order to reduce the amount of exo-end compound and end-end compound in the compound represented by the formula (20), a method for precision distillation of the compound represented by the formula (20), column chromatography using silica gel or the like as a filler is used. Any method can be applied, such as the method of applying the technique.

When the composition (X) contains the polyfunctional cationically polymerizable compound (W11), the ratio of the polyfunctional cationically polymerizable compound (W11) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. .. The resin component refers to a cationically polymerizable compound in the composition (X), and includes a polyfunctional cationically polymerizable compound (W1) and a monofunctional cationically polymerizable compound (W2). When the proportion of the polyfunctional cationically polymerizable compound (W11) is 5% by mass or more, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product has high strength. Can have (hardness). Further, when the ratio of the polyfunctional cationically polymerizable compound (W11) is 95% by mass or less, when the composition (X) contains the hygroscopic agent (F), the hygroscopic agent (F) is contained in the composition (X). ) Can be dispersed with particularly high uniformity. The proportion of the polyfunctional cationically polymerizable compound (W11) is more preferably 12% by mass or more, further preferably 15% by mass or more, further preferably 20% by mass or more, and 25% by mass or more. Is particularly preferable. The proportion of the polyfunctional cationically polymerizable compound (W11) is more preferably 85% by mass or less, and further preferably 60% by mass or less. For example, the proportion of the polyfunctional cationically polymerizable compound (W11) is preferably in the range of 20 to 60% by mass.

When the polyfunctional cationically polymerizable compound (W11) contains a polyfunctional alicyclic epoxy compound, the polyfunctional alicyclic epoxy compound may be a part of the polyfunctional cationically polymerizable compound (W11), and all of them may be. May be. The ratio of the polyfunctional alicyclic epoxy compound to the polyfunctional cationically polymerizable compound (W11) is preferably in the range of 15 to 100% by mass. When this ratio is 15% by mass or more, the polyfunctional alicyclic epoxy compound can particularly contribute to the improvement of 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, and more preferably 2 to 4. The polyfunctional cationically polymerizable compound (W12) can contribute to the improvement of the cationic polymerization reactivity of the composition (X) and the heat-resistant discoloration of the cured product and the optical component. The polyfunctional cationically polymerizable compound (W12) can also contribute to lowering the elastic modulus of the cured product and the optical component. When the composition (X) contains a hygroscopic agent, the polyfunctional cationically polymerizable compound (W12) can also contribute to the improvement of the dispersibility of the hygroscopic agent in the composition (X) and the cured product.

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

The cationically polymerizable functional group contained in the polyfunctional cationically polymerizable compound (W12) is at least one group selected from the group consisting of, for example, 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 in the range of 2 to 14. In this case, the composition (X) can have a particularly low viscosity. The number of Si atoms is more preferably in the range of 2 to 10, further preferably in the range of 2 to 7, and particularly preferably in the range of 3 to 6.

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

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

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

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

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

More specifically, the polyfunctional cationically polymerizable compound (W12) is, for example, product numbers 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 preferable.

The polyfunctional cationically polymerizable compound (W12) preferably has an alicyclic epoxy structure, and it is particularly preferable that the polyfunctional cationically polymerizable compound (W12) contains the compound represented by the formula (10a). The compound represented by the formula (10a) can particularly contribute to the improvement of the cationic polymerization reactivity and the reduction of the viscosity of the composition (X), and particularly to the improvement of the heat-resistant discoloration property and the low elastic modulus of the cured product and the optical component. Can contribute. When the composition (X) contains the hygroscopic agent (F), it can particularly contribute to the improvement of the dispersibility of the hygroscopic agent (F) in the composition (X).

When the composition (X) contains the polyfunctional cationically polymerizable compound (W12), the ratio of the polyfunctional cationically polymerizable compound (W12) to the total amount of the resin component is preferably in the range of 5 to 95% by mass. .. In this case, particularly when the composition (X) contains the hygroscopic agent (F), the dispersibility of the hygroscopic agent (F) in the composition (X) and the cured product is particularly improved, and the composition (X) Can have a particularly high photocationic polymerization reactivity.

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

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

The monofunctional cationically polymerizable compound (W2) can contain, for example, at least one compound selected from the group consisting of the 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 the resin component is preferably in the range of 5 to 50% by mass. When the proportion of the monofunctional cationically polymerizable compound (W2) is 5% by mass or more, the viscosity of the composition (X) can be particularly reduced. Further, when the proportion of the monofunctional cationically polymerizable compound (W2) is 50% by mass or less, the composition (X) can have particularly excellent reactivity during the photocationic polymerization reaction, whereby the cured product can be obtained. Can have high strength (hardness). The ratio of the monofunctional cationically polymerizable compound (W2) is more preferably 10% by mass or more, still more preferably 15% by mass or more. The proportion of the monofunctional cationically polymerizable compound (W2) is more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less. When the proportion of the monofunctional cationically polymerizable compound (W2) is particularly 35% by mass or less, the amount of volatilization of the components in the composition (X) during storage of the composition (X) can be effectively reduced. Therefore, even if the composition (X) is stored for a long period of time, the characteristics of the composition (X) are not easily impaired. Further, it is possible to particularly suppress the occurrence of tack on the cured product. For example, the proportion of the monofunctional cationically polymerizable compound (W2) is preferably in the range of 10 to 35% by mass.

Further, particularly when the composition (X) contains the polyfunctional cationically polymerizable compound (W11) and the polyfunctional cationically polymerizable compound (W12), the polyfunctional cationically polymerizable compound (W11) is used with respect to the total amount of the resin component. The ratio of the polyfunctional cationically polymerizable compound (W12) is in the range of 15 to 30% by mass, and the ratio of the monofunctional cationically polymerizable compound (W2) is 15 to 40% by mass. It is preferably in the range of%. In this case, good storage stability of the composition (X), low viscosity, and good cationic polymerization reactivity can be achieved in a well-balanced manner, and further, excellent transparency of the cured product and excellent hygroscopicity can be achieved in a well-balanced manner. ..

If the cationically polymerizable compound (A12) contains the compound represented by the formula (3) and the compound represented by the formula (16), a photocured product is produced from the composition (X) by adjusting the ratio of both. It is possible to reduce the viscosity of the composition (X) and improve the storage stability while appropriately adjusting the ease of progress of the curing reaction in the case of the above.

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

The cationically polymerizable compound (A12) 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 glucol group, and when there are a plurality of X in one molecule, they are different even if they are the same. You may. The hydrocarbon group is, for example, an alkyl group or an aryl group. When X is a hydrocarbon group, the number of carbon atoms of X is, for example, in the range of 1 to 10. R is a single bond or 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 (for example, -CO-O-CH2-), or -C (Ph) 2-O-. CH2-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 cationically polymerizable compound (A12) contains the aromatic epoxy compound (f1), the aromatic epoxy compound (f1) has a low viscosity, so that the aromatic epoxy compound (f1) lowers the viscosity of the composition (X). I can let you. Further, the aromatic epoxy compound (f1) is less likely to volatilize, so that even if the composition (X) is stored, the composition (X) is less likely to change in composition due to the volatilization of the aromatic epoxy compound (f1). .. Therefore, the aromatic epoxy compound (f1) can enhance the storage stability of the composition (X). Further, since the aromatic epoxy compound (f1) has high reactivity, unreacted components are less likely to remain in the cured product, and therefore outgas is less likely to be generated from the cured product. Further, the aromatic epoxy compound (f1) can increase the glass transition temperature of the cured product, and thus can increase the heat resistance of the cured product.

Further, the aromatic epoxy compound (f1) is less likely to generate defective droplets called satellites when the composition (X) is ejected by the inkjet method. A satellite is a droplet that is separated from the original droplet and adheres to a position different from the original droplet attachment position on the coating target when the droplet is ejected by the inkjet method. When satellites are generated, the dimensional accuracy of the cured product produced from the composition (X) is deteriorated.

It is preferable that R in the formula (30) is a single bond or an alkylene group. When n in the formula (30) is 2 or 3, it is preferable that at least one of the plurality of Rs in the formula (30) is a single bond or an alkylene group. In these cases, the reactivity of the aromatic epoxy compound (f1) becomes high, and therefore the curability of the composition (X) when the composition (X) is irradiated with ultraviolet rays can be high.

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

In particular, the aromatic epoxy compound (f1) may contain at least one component selected from the group consisting of the compounds represented by the formulas (301) to (305), (312), (314) and (318), respectively. preferable. These compounds have high reactivity because at least one epoxy group (oxylan) in the compound and a benze ring are bonded by a single bond or an alkylene group, and thus the curability of the composition (X). Can be enhanced.

The ratio of the aromatic epoxy compound (f1) to the entire cationically polymerizable compound (A12) is preferably 5% by mass or more. In this case, the above-mentioned action by the aromatic epoxy compound (f1) can be obtained particularly remarkably. This ratio is also preferably 95% by mass or less. In this case, the storage stability of the composition (X) may be good. This ratio is more preferably 10% by mass or more and 90% by mass or less, and further preferably 20% by mass or more and 85% by mass or less.

It is also preferable that the cationically polymerizable compound (A12) 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 cationically polymerizable compound (A12) contains the compound (f2), the compound (f2) has a low viscosity, so that the compound (f2) can reduce the viscosity of the composition (X). Further, the compound (f2) is less likely to volatilize, and therefore, even if the composition (X) is stored, the composition (X) is less likely to change in composition due to the volatilization of the aromatic epoxy compound (f1). Therefore, the compound (f2) can enhance the storage stability of the composition (X).

Further, the compound (f2) is less likely to generate defective droplets called satellites when the composition (X) is ejected by the inkjet method. Further, the compound (f2) can make satellites less likely to occur even if the speed of the droplets ejected by the inkjet method is increased. Therefore, depending on the conditions of inkjet, for example, it is possible to increase the ejection speed of droplets by the inkjet method to 4 m / s or more without causing satellites. If the velocity of the droplet can be increased, the trajectory of the droplet is less likely to be affected by disturbance, so that the dimensional accuracy of the cured product produced from the composition (X) can be improved. Further, since the compound (f2) can enhance the storage stability of the composition (X) as described above, the composition (X) is less likely to generate satellites even if the composition (X) is stored for a long period of time. The properties can be maintained.

The oxyalkylene skeleton preferably contains a structure of "-C-C-O-", that is, an oximethylene unit. In this case, satellites are less likely to be generated, and satellites are less likely to be generated even if the drive frequency at which the composition (X) is ejected by, for example, an inkjet method is changed. Further, the compound (f2) is less likely to volatilize and has a lower viscosity, and the affinity (wetting property) of the composition (X) with respect to the inorganic material can be enhanced.

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) can have a lower viscosity, satellites are less likely to occur, and the crosslink density of the cured product can be increased, so that the glass transition temperature of the cured product can be particularly high. The number of the oxyalkylene units is more preferably 1 or more and 6 or less, and further preferably 1 or more and 4 or less.

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

The ratio of the compound (f2) is preferably 10% by mass or more with respect to the cationically polymerizable compound (A12). In this case, the ink jet property becomes good and the wettability to the base material becomes good. It is also preferable that this ratio is 70% by weight or less. In this case, the glass transition temperature can be sufficiently increased. This ratio is more preferably 15% by mass or more and 60% by mass or less, and further preferably 20% by mass or more and 50% by mass or less.

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

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

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

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. The compound having sulfur is particularly preferable to contain a compound having a phenyl sulfide skeleton. The phenyl sulfide skeleton is a structure in which a phenyl group and a sulfur atom are directly bonded by a single bond. The compound having a phenyl sulfide skeleton preferably contains a polyarylene sulfide compound. The 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 a bis (4-methacryloylthiophenyl) sulfide that does not easily generate an odor. The ratio of the compound having sulfur to the photocurable compound (A1) 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. ..

It is also preferable that the cationically polymerizable compound (A12) contains an epoxy compound and the above-mentioned compound (f22). The epoxy compound contains, for example, at least one compound among the compounds having an epoxy group among the compounds that can be contained in the above-mentioned cationically polymerizable compound (A12). When the cationically polymerizable compound (A12) contains the epoxy compound and the compound (f22), the curability of the composition (X) when the composition (X) is irradiated with ultraviolet rays is enhanced, and the composition at this time is enhanced. Too rapid curing of (X) is less likely to occur, and therefore deterioration of transparency due to cloudiness or the like is less likely to occur in the cured product. 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 first reacts. The reaction of this epoxy compound can 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 once. It is considered 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 (A12) is preferably 20% by mass or more. In this case, the compound (f22) can make the composition (X) particularly low in viscosity and particularly enhance the storage stability of the composition (X). Further, the compound (f22) can particularly enhance the curability of the composition (X). The proportion of the compound (f22) is also preferably 90% by mass or less. In this case, the curability of the cured product can be sufficiently enhanced. The ratio of the compound (f22) is more preferably 10% by mass or more and 90% by mass or less, and further preferably 20% by mass or more and 80% by mass or less. Further, the ratio of the epoxy compound in this case is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less with respect to the total amount of the cationically polymerizable compound (A12). , 25% by mass or more and 75% by mass or less is more preferable. In these cases, the unreacted groups in the cured product can be sufficiently reduced to sufficiently enhance the curability of the cured product.

The epoxy compound preferably contains a compound having at least one oxylan ring that does not form a glycidyl ether group. In this case, the epoxy compound can particularly enhance the curability of the composition (X). It is more preferable that the epoxy compound contains a compound having two or more oxylane rings that do not form a glycidyl ether group. It is also preferable that the epoxy compound contains a compound having no glycidyl ether group. It is particularly preferable that the epoxy compound contains a compound having two or more oxylane rings that do not form a glycidyl ether group and that does not have a glycidyl ether group.

It is particularly preferable that the cationically polymerizable compound (A12) contains the compound (f2) and the epoxy compound, and the epoxy compound further contains the above-mentioned aromatic epoxy compound (f1). In this case, the composition (X) has particularly excellent storage stability, and when the composition (X) is ejected by an inkjet method, it is particularly difficult to generate defective droplets called satellites. Further, even if the speed of the droplets ejected by the inkjet method is increased, satellites can be made particularly difficult to occur. Further, even if the composition (X) is stored for a long period of time, the characteristic of the composition (X) that satellites are less likely to be generated can be particularly maintained. In this case, it is particularly preferable that the compound (f2) contains the compound (f22).

The total ratio of the aromatic epoxy compound (f1) and the compound (f22) to the cationically polymerizable compound (A12) is preferably 55% by mass or more. In this case, the action of the combination of the aromatic epoxy compound (f1) and the compound (f22) is particularly remarkable. This ratio is more preferably 60% by mass or more, and further preferably 70% by mass or more. It is particularly preferable that the cationically polymerizable compound (A12) contains only the aromatic epoxy compound (f1) and the compound (f22).

When the composition (X) contains the cationically polymerizable compound (A12), it is preferable that the composition (X) further contains a sensitizer. In this case, the composition (X) can have a particularly high cationic polymerization reactivity. The sensitizer contains, for example, one or both of 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene. The ratio of the sensitizer to the cationically polymerizable compound (A12) is preferably more than 0% by mass and preferably in the range of 1% by mass or less. In this case, the sensitizer does not easily impair the transparency of the cured product, so that the cured product can have good transparency.

When the composition (X) contains a cationically polymerizable compound (A12), it is preferable that the composition (X) further contains a photocationic polymerization initiator (E2). The photocationic polymerization initiator (E2) is not particularly limited as long as it is a catalyst that generates protonic acid or Lewis acid by being irradiated with light. The photocationic polymerization initiator (E2) can contain at least one of an ionic photoacid generation type cation curing catalyst and a nonionic photoacid generation type cation curing catalyst.

The ionic photoacid generation type cationic curing catalyst can contain at least one of an onium salt and an organic metal complex. Examples of onium salts include aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts. Examples of organometallic complexes include iron-allene complexes, titanosen complexes, and arylsilanol-aluminum complexes. The ionic photoacid generation type cationic curing catalyst can contain at least one of these components.

The nonionic photoacid generation type cationic curing catalyst is at least one selected from the group consisting of, for example, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide phosphonate. Can contain the components of. The components that can be contained in the nonionic photoacid generation type cationic curing catalyst are not limited to the above.

More specific examples of compounds that can be contained in the photocationic polymerization initiator (E2) are DPI series (105, 106, 109, 201, etc.), BI-105, MPI series (103, 105, 106, etc.) manufactured by Midori Kagaku. 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, etc.) , 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, etc.) , 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-Actate, DTS-Actate, Di-Boc Bisphinol A, tert-Butyl lithocholate, tert-Butyl deoxycholate, tert-Butyl cholate, BX, BC-2, MPI-103, BDS-105, TP -103, BMS-105, and TMS-105;
Union Carbide, USA Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, and Cyracure UVI-950;
BASF's Irgacure 250, Irgacure 261 and Irgacure 264;
CG-24-61 manufactured by Ciba Geigy Co., Ltd .;
ADEKA CORPORATION ADEKA CORPORATION SP-150, ADEKA CORPORATION SP-151, ADEKA CORPORATION SP-170 and ADEKA CORPORATION SP-171;
DAICAT II manufactured by Daicel Corporation;
UVAC1590 and UVAC1591 manufactured by Daicel Cytec Co., Ltd .;
CI-2064, CI-2369, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, and CIT-1682; manufactured by Nippon Soda Corporation;
PI-2074, a tetrakis (pentafluorophenyl) borate toluyl cumyliodonium salt manufactured by Rhodia;
3M FFC509;
CD-1010, CD-1011 and CD-1012 manufactured by Sartomer, USA;
Includes CPI-100P, CPI-101A, CPI-110P, CPI-110A and CPI-210S from Sun Appro Co., Ltd .; and UVI-6992 and UVI-6976 from Dow Chemical. The photocationic polymerization initiator (E2) can contain at least one compound selected from the group consisting of these compounds.

The ratio of the photocationic polymerization initiator (E2) to the cationically polymerizable compound (A12) is preferably in the range of 1 to 4% by mass. When this ratio is 1% by mass or more, the composition (X) can have a particularly good cationic polymerization reactivity. Further, when this ratio is 4% by mass or less, the composition (X) can have good storage stability, and the production cost is reduced by not containing an excessive photocationic polymerization initiator (E2). Is possible.

<Fluorescent body (B)>
Next, the fluorescent substance (B) will be described. The fluorophore (B) preferably contains a quantum dot fluorophore (B1). When the phosphor (B) contains the quantum dot phosphor (B1), 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 possible to realize a wide color gamut of the light emitted from the filter 2. Therefore, it is possible to realize a wide color gamut of the light emitted from the light emitting device 11 including the color filter 2, particularly the display device. Further, since the wide color gamut can be realized by the color filter 2, it is not necessary to separately provide a member such as a filter for widening the color gamut in the light emitting device 11, particularly the display device. Therefore, it is possible to suppress an increase in the number of parts of the light emitting device 11 (display device) in widening the color gamut. Therefore, the light emitting device 11 (display device) can be made thinner, and for example, a bendable flexible light emitting device 11 (display device) can be realized.

Quantum dots are semiconductor particles that exhibit a quantum size effect, and quantum dot phosphors (B1) are phosphors composed of quantum dots. The average particle size of the quantum dot phosphor (B1) is, for example, 1 nm or more and 10 nm or less. The average particle size of the quantum dot phosphor (B1) is preferably 2 nm or more and 6 nm or less. Even if the quantum dot phosphor (B1) has the same composition, the wavelength of fluorescence emitted differs depending on the particle size. Therefore, it is preferable that the quantum dot phosphor (B1) has a particle size corresponding to the wavelength of fluorescence emitted by the wavelength conversion member produced from the composition (X). The quantum dot phosphor (B1) contains at least one semiconductor particle selected from the group consisting of, for example, a semiconductor particle that emits red fluorescence, a semiconductor particle that emits green fluorescence, and a semiconductor particle that emits blue fluorescence. do. The quantum dot phosphor (B1) may contain semiconductor particles that fluoresce in colors other than these.

The average particle size of the quantum dot phosphor (B1) is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As the measuring device, Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

The quantum dot phosphor (B1) may contain semiconductor particles having a core-shell structure. Specifically, the quantum dot phosphor (B1) contains semiconductor particles (CdSe / ZnS) having, for example, a core made of CdSe and a shell made of ZnS. The quantum dot phosphor (B1) may contain other suitable semiconductor particles. For example, the quantum dot phosphor (B1) is a GaN, GaP, InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ , In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO, CdS, or perovskite type semiconductor. And may contain semiconductor particles having at least one semiconductor selected from the group consisting of graphene type semiconductors. The semiconductor particles that the quantum dot phosphor (B1) can contain are not limited to the above.

The amount of the quantum dot phosphor (B1) in the composition (X) is, for example, 0.1% by mass or more and 40% by mass or less with respect to the entire composition (X). When the amount of the quantum dot phosphor (B1) is 0.1% by mass or more, the cured product of the composition (X) can exhibit the wavelength conversion function. Further, when the amount of the quantum dot phosphor (B1) is 40% by mass or less, the composition (X) can be molded by an inkjet method. The amount of the quantum dot phosphor (B1) is more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. The amount of the quantum dot phosphor (B1) is more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less.

<Light scattering particles (C)>
Next, the light scattering particles (C) will be described.

First, the light scattering particles (C) used in the first embodiment will be described. In the first embodiment, as described above, the light scattering particles (C) are core-shell type particles having a core portion having a specific gravity of 2.0 or less and a shell having a refractive index of 1.9 or more covering the core portion. (C0) is included. The light scattering particles (C) may be all core-shell type particles (C0) or may include some particles of other species having a light scattering function.

Since the core-shell type particles (C0) have a specific gravity of 2.0 or less in the core portion, they are relatively difficult to settle in the composition (X). Further, since the refractive index of the shell is 1.9 or more, the difference in the refractive index between the core-shell type particles (C0) and the cured product of the reaction-curable compound (A) in the wavelength conversion member becomes large, and therefore the wavelength. The light incident on the conversion member can be reflected at the interface between the core-shell type particles (C0) and the cured product of the reaction-curable compound (A). Therefore, light may be scattered in the wavelength conversion member.

The specific gravity of the core portion is more preferably 1.2 or less, and further preferably 0.8 or less. Further, the specific gravity of the core portion is, for example, 0.1 or more.

The core portion may be composed of tangible particles (core particles) or may be a hollow portion having a void shape.

The core particles may contain at least one of organic resin particles and inorganic particles. In particular, when the core particles contain organic resin particles, the specific gravity of the core portion can be reduced. The organic resin particles include, for example, at least one resin selected from the group consisting of acrylic resins, styrene resins and copolymers thereof, and urethane resins.

The core particles may contain hollow particles. Hollow particles are particles containing voids. When the core particles contain hollow particles, the specific gravity of the core portion can be reduced. Further, when the core particles contain hollow particles, when the light incident on the wavelength conversion member is incident on the hollow particles, the light is reflected at the interface between the solid and the gas in the hollow particles, and therefore light is scattered. Particles (C) can further scatter light.

The hollow particles may contain at least one of organic resin particles (hollow resin particles) and inorganic particles (hollow inorganic particles). The hollow resin particles contain at least one selected from the group consisting of, for example, hollow acrylic resin particles, hollow styrene resin particles, and the like. The hollow inorganic particles contain at least one selected from the group consisting of, for example, hollow silica particles, hollow glass particles, and hollow alumina particles, hollow alumina silicate particles, hollow calcium carbonate particles, and the like.

As mentioned above, the refractive index of the shell is 1.9 or more. The refractive index of the shell is more preferably 2.2 or more, and even more preferably 2.5 or more. The higher the refractive index of the shell is, the more preferable it is, and the upper limit is not particularly limited. For example, the refractive index of the shell is 4.0 or less.

Further, the refractive index of the shell is preferably 0.4 or more higher than the refractive index of the cured product of the reaction-curable compound (A). That is, the refractive index of the shell is higher than the refractive index of the reaction-curable compound (A), and the difference in refractive index between the shell and the cured product of the reaction-curable compound (A) is 0.4 or more. preferable. In this case, light can be particularly reflected at the interface between the light-scattering particles (C) and the cured product of the reaction-curable compound (A). The difference in refractive index is more preferably 0.7 or more, and even more preferably 1.0 or more. The larger the difference in refractive index is, the more preferable it is, but the difference in refractive index is, for example, 2.5 or less.

The material of the shell is appropriately selected according to the refractive index required for the shell. The shell contains, for example, at least one selected from the group consisting of titanium oxide, zinc oxide, zirconium oxide, aluminum oxide and barium titanate. In this case, a high refractive index difference can be realized.

The shell may cover at least a part of the surface of the core particles. Preferably, the shell covers more than 50% of the surface of the core particles. In this case, the light scattering particles (C) can particularly scatter the light. It is particularly preferable that the shell covers the entire surface of the core particles.

When the core portion is a hollow portion, core-shell type particles (C0) are produced, for example, as follows. Raw material particles are produced by covering the organic resin particles with a shell. The structure of the shell may be the same as when the core portion is a core particle. The raw material particles are heated, for example, at a temperature of 900 ° C. or higher. Then, the particles of the organic resin evaporate to obtain core-shell type particles (C0) having the shell and the hollow portion inside the shell. In this case, the crystallinity of the shell can be increased by heating the shell, whereby the refractive index of the shell can be increased. Further, by increasing the hollowness ratio of the core-shell type particles (C0), the specific gravity of the light-scattering particles (C) can be lowered, and therefore the light-scattering particles (C) can be less likely to settle.

It is also preferable that the thickness of the shell is 5 nm or more and 60 nm or less. When the thickness is 5 nm or more, light can be particularly reflected at the interface between the core-shell type particles (C0) and the cured product. Further, when the thickness is 60 nm or less, the core-shell type particles (C0) are particularly difficult to settle. The thickness is more preferably 10 nm or more, and further preferably 20 nm or more from the viewpoint of light scattering. Further, the thickness is more preferably 40 nm or less, and further preferably 30 nm or less from the viewpoint of sedimentation.

The core-shell type particles (C0) may further include at least one of a silica film and an alumina film covering the shell. In this case, particularly when the reaction-curable compound (A) has photocationic polymerizable properties in the composition (X), the shell inhibits the photocationic polymerization reaction of the reaction-curable compound (A). It can be suppressed by a silica film and an alumina film. Therefore, the light-scattering particles (C) are unlikely to reduce the reactivity of the reaction-curable compound (A). The thickness of each of the silica film and the alumina film is preferably sufficiently small so that the silica film and the alumina film do not interfere with the action of the light scattering particles (C) to scatter light. Instead of the silica film and the alumina film, the core-shell type particles (C0) may be provided with an appropriate film that does not inhibit the photocationic polymerization reaction like the silica film and the alumina film.

The specific gravity of the core-shell type particles (C0) is preferably 1.5 or less. In this case, the core-shell type particles (C0) are less likely to settle in the composition (X). This specific gravity is more preferably 1.3 or less, and even more preferably 1.2 or less. Further, this specific gravity is, for example, 0.9 or more.

The average particle size of the core-shell type particles (C0) is preferably 0.1 μm or more and 1 μm or less. When the average particle size is 0.1 nm or more, the core-shell type particles (C0) can effectively scatter light. When the average particle size is 1 μm or less, the core-shell type particles (C0) are particularly dispersed in the composition (X), so that the core-shell type particles (C0) are particularly difficult to settle. Further, when the average particle size is 1 μm or less, particularly when the composition (X) is formed by an inkjet method, it is possible to prevent damage to the device due to clogging or adhesion of the composition (X) in the inkjet device. The average particle size is more preferably 0.15 μm or more, and even more preferably 0.2 μm or more. Further, the average particle size is more preferably 0.8 μm or less, and further preferably 0.5 μm or less. The average particle size referred to here is a median diameter calculated from the particle size distribution measured by the dynamic light scattering method. As the measuring device, Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

Next, the light scattering particles (C) used in the second embodiment will be described.

In the second embodiment, the light scattering particles (C) contain titanium oxide particles (C1) and hollow particles (C2) as described above.

The titanium oxide particles (C1) have a high refractive index, so that light can be refracted or reflected at the interface between the titanium oxide particles (C1) and the resin. Therefore, the titanium oxide particles (C1) can reflect light.

The average particle size of the titanium oxide particles (C1) is preferably 300 nm or less. In this case, sedimentation of the light-scattering particles (C) is particularly unlikely to occur. The average particle size is more preferably 290 nm or less, further preferably 260 nm or less, and particularly preferably 230 nm or less. It is also preferable that the average particle size of the titanium oxide particles (C1) is 50 nm or more. In this case, the light scattering performance of the titanium oxide particles (C1) can be particularly exhibited. The average particle size is more preferably 80 nm or more, and even more preferably 100 nm or more. The average particle size of the titanium oxide particles (C1) is a median diameter calculated from the particle size distribution obtained from the measurement results by the dynamic light scattering method. As the measuring device, for example, Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

The hollow particles (C2) have a shell portion and a hollow portion inside the shell portion. Therefore, the refractive index changes discontinuously at the interface between the shell portion and the hollow portion inside the hollow particles (C2). Therefore, the hollow particles (C2) can scatter light. Further, since the hollow particles (C2) have a hollow portion, the specific gravity is small, and therefore it is difficult to settle in the composition (X). Therefore, the hollow particles (C2) do not easily impair the storage stability of the composition (X). Further, as described above, the hollow particles (C2) can also suppress the sedimentation of the titanium oxide particles (C1).

The specific gravity of the hollow particles (C2) is preferably 0.2 or more and 1.2 or less. When the specific gravity is 1.2 or less, the hollow particles (C2) are particularly unlikely to settle in the composition (X), and therefore the storage stability of the composition (X) is not particularly impaired. Further, when the specific gravity is 0.2 or more, the phenomenon that the hollow particles (C2) float on the surface at the time of curing is suppressed, the composition of the cured product is made uniform, the physical strength is high, and the hollow particles (hollow particles (C2)). Damage to C2) is also 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 further preferably 0.4 or more.

The hollow particles (C2) can contain at least one of the hollow resin particles (C21) and the hollow inorganic particles (C22). The shell portion of the hollow resin particles (C21) is made of resin, and the shell portion of the hollow inorganic particles (C22) is made of an inorganic material.

When the hollow particles (C2) contain the hollow resin particles (C21), the hollow resin particles (C21) do not easily impair the light transmittance of the cured product of the composition (X). Therefore, the light transmittance of the wavelength conversion member can be maintained. Further, the hollow resin particles (C21) are not easily damaged even if a force is applied in a process such as kneading when preparing the composition (X) and a process of producing a cured product from the composition (X). The hollow resin particles (C21) contain at least one selected from the group consisting of, for example, hollow acrylic resin particles and hollow styrene resin particles.

When the hollow particles (C2) contain hollow inorganic particles (C22), the shell portion of the hollow inorganic particles (C22) may be, for example, silica, silicate glass, alumina, alumina silicate, calcium carbonate, titania (titanium oxide) or the like. Contains at least one selected from the group consisting of. When the shell portion contains at least one of silica and silicate glass, for example, when the hollow inorganic particles (C22) contain at least one of hollow silica particles and hollow glass particles, the hollow inorganic particles (C22) The light transmittance of the cured product of the composition (X) is not easily impaired. When the hollow particles (C2) contain particles containing titania (for example, hollow titania particles), the particles containing titania do not correspond to titanium oxide particles (C1).

The average particle size of the hollow particles (C2) is preferably 100 nm or more and 3 μm or less. When the average particle size is 100 nm or more, the hollow particles (C2) can effectively scatter light. When the average particle size is 3 μm or less, it is possible to prevent damage to the device due to clogging or adhesion of the composition (X) in the inkjet device. The average particle size is more preferably 150 nm or more, and even more preferably 1 μm or more. Further, the average particle size is more preferably 800 nm or less, and further preferably 500 nm or less. The average particle size of the hollow particles (C2) is a median diameter calculated from the particle size distribution obtained from the measurement result by the dynamic light scattering method. As the measuring device, for example, Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

The average particle size of the hollow particles (C2) is preferably 1 to 15 times the average particle size of the titanium oxide particles (C1). In this case, the sedimentation of the titanium oxide particles (C1) is particularly suppressed, and the storage stability of the composition (X) is further enhanced. This magnification is more preferably 1.5 times or more, and even more preferably 2.0 times or more. Further, this magnification is more preferably 10 times or less, and further preferably 7 times or less.

In particular, the average particle size of the hollow resin particles (C21) is preferably 1.5 times or more the average particle size of the titanium oxide particles (C1). In this case, the sedimentation of the titanium oxide particles (C1) is particularly suppressed. This magnification is more preferably 1.8 times or more, and even more preferably 2.0 times or more. Further, this magnification is, for example, 10 times or less.

Further, the average particle size of the hollow inorganic particles (C22) is preferably 220 nm or more. Further, the average particle size is preferably twice or more the average particle size of the titanium oxide particles (C1). In this case, the sedimentation of the titanium oxide particles (C1) is particularly suppressed. It is more preferable that the average particle size is 300 nm or more. The average particle size is, for example, 1000 nm or less. Further, the magnification of the average particle size is more preferably 10 times or less, and further preferably 7 times or less.

The percentage of the hollow particles (C2) to the total of the titanium oxide particles (C1) and the hollow particles (C2) is preferably 10% by volume or more and less than 100% by volume. When this percentage is 10% by volume or more, sedimentation of the light-scattering particles (C) is particularly unlikely to occur. Further, if this percentage is less than 100% by volume, the light-scattering particles (C) can scatter light more effectively. This percentage is more preferably 15% by volume or more, and even more preferably 30% by volume or more. Further, this percentage is more preferably 85% by volume or less, further preferably 70% by volume or less, and further preferably 50% by volume or less.

In a preferred embodiment of the present disclosure, the percentage of the light-scattering particles (C) to the solid content in the composition (X) is preferably 1% by volume or more and 30% by volume or less. When this percentage is 1% by volume or more, the light-scattering particles (C) can scatter light more effectively. When this percentage is 30% by volume or less, the inkjet property of the composition (X) can be improved. The lower side of this percentage is more preferably 5% by volume or more, and even more preferably 10% by volume or more. Further, the upper side of this percentage is more preferably 25% by volume or less, and further preferably 20% by volume or less. The percentage may be 18% by volume or less, and further may be 15% by volume or less.

In particular, in the first embodiment, the percentage of the core-shell type particles (C0) to the solid content in the composition (X) is preferably 1% by volume or more and 20% by volume or less. The solid content is a component in the composition (X) excluding the solvent. When the percentage is 1% by volume or more, the core-shell type particles (C0) can scatter light more effectively. When the percentage is 20% by volume or less, the ink jet property can be improved particularly when the composition (X) is molded by the ink jet method. This percentage is more preferably 5% by volume or more, and even more preferably 10% by volume or more. Further, this percentage is more preferably 18% by volume or less, and further preferably 15% by volume or less.

Further, particularly in the second embodiment, the percentage of the titanium oxide particles (C1) to the solid content in the composition (X) is preferably 1% by volume or more and 20% by volume or less. When this percentage is 1% by volume or more, the titanium oxide particles (C1) can scatter light more effectively. When this percentage is 20% by volume or less, the inkjet property of the composition (X) is good, and the precipitation of the light scattering particles (C) is particularly unlikely to occur. This percentage is more preferably 5% by volume or more, and even more preferably 8% by volume or more. Further, this percentage is more preferably 15% by volume or less, and further preferably 12% by volume or less.

Further, the percentage of the hollow particles (C2) to the solid content in the composition (X) is preferably 0.1% by volume or more and 20% by volume or less. When this percentage is 0.1% by volume or more, sedimentation of the light scattering particles (C) is particularly unlikely to occur. When this percentage is 20% by volume or less, the inkjet property of the composition (X) can be improved. This percentage is more preferably 1% by volume or more, and even more preferably 10% by mass or more.

<Dispersant (D)>
In a preferred embodiment of the present disclosure, the composition (X) preferably contains a dispersant (D). The dispersant (D) can improve the dispersibility of the fluorophore (B) in the composition (X). Therefore, the dispersant (D) can prevent the increase in viscosity of the composition (X) and the decrease in storage stability due to the fluorescent substance (B). Further, the dispersant (D) can enhance the dispersibility of the light-scattering particles (C) in the composition (X). Therefore, the light-scattering particles (C) are less likely to settle.

In particular, when the light-scattering particles (C) contain titanium oxide particles (C1) and hollow particles (C2) as in the second embodiment, the dispersant (D) disperses the light-scattering particles (C). It can greatly enhance the sex. It is presumed that this is because the dispersant (D) enhances the interaction between the titanium oxide particles (C1) and the hollow particles (C2).

The dispersant (D) is a surfactant that can be adsorbed on the particles. The dispersant (D) generally has an adsorbing group (also referred to as an anchor) that can be adsorbed on the particles and a molecular skeleton (also referred to as a tail) that adheres to the particles when the adsorbing group is adsorbed on the particles. The dispersant (D) is, for example, an acrylic dispersant having an acrylic molecular chain at the tail, a urethane dispersant having a urethane molecular chain at the tail, and a polyester-based dispersion having a polyester molecular chain at the tail. It contains at least one ingredient selected from the group if it is an agent. The adsorbent group contains, 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 (D) may contain a polymer. The weight average molecular weight of the polymer is, for example, 1000 or more. Examples of the polymer include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high-molecular-weight acid ester, a salt of a high-molecular-weight polycarboxylic acid, a salt of a long-chain polyaminoamide and a polar acid ester, and a high-molecular-weight unsaturated acid ester. , Modified polyurethane, modified polyacrylate, polyether ester type anionic activator, salt of naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonylphenyl ether, polyester polyamine, and stearylamine acetate. Contains at least one ingredient selected from the group. When the dispersant (D) contains a polymer, the dispersibility of the light-scattering particles (C) can be further enhanced. For example, in the case of the second embodiment, it is presumed that the titanium oxide particles (C1) are more likely to be entangled with the molecular chain of the polymer, which makes it more difficult for the titanium oxide particles (C1) to settle.

The dispersant (D) preferably contains a dispersant (D1) having two or more adsorbent groups in one molecule. In this case, the dispersant (D) can more disperse the light scattering particles (C). For example, in the case of the second embodiment, the dispersant (D1) has two or more adsorbing groups, so that the dispersant (D1) is composed of titanium oxide particles (C1) and hollow particles (C2). It is presumed that this is because it becomes easier to mediate the interaction, and therefore the titanium oxide particles (C1) are less likely to settle.

The dispersant (D1) can contain at least one selected from the group consisting of, for example, a two-terminal dispersant, a comb-type dispersant, a side chain-terminal dispersant, and a super-branched dispersant. The bi-terminal dispersant has a structure in which adsorbents are bonded to both ends of the tail. The comb-type dispersant has a structure in which a plurality of adsorbing groups are present in the main chain of a comb-shaped tail having a main chain and a plurality of side chains. The side chain terminal dispersant has a structure in which an adsorbent group is bonded to the end of the side chain of the tail having a main chain and a plurality of side chains, or an adsorbent group is further bonded to one or both ends of the main chain. .. The super-branched dispersant has a structure in which a nucleus having an adsorbent group is covered with a branched tail.

When the dispersant (D1) contains at least one selected from the group consisting of a two-terminal dispersant, a comb-type dispersant, and a side chain terminal dispersant, the dispersant (D) contains the viscosity of the composition (X). Is difficult to raise. When the dispersant (D) contains a bi-terminal dispersant, the dispersant (D1) is particularly difficult to increase the viscosity of the composition (X). If the dispersant (D1) is difficult to increase the viscosity of the composition (X), the degree of freedom in selecting components other than the dispersant (D1) is increased. A component that can improve the function can be blended into the composition (X), and the viscosity of the composition (X) can be kept low.

The viscosity of the dispersant (D) is preferably 50,000 mPa · s or less. In this case, the dispersant (D) does not easily increase the viscosity of the composition (X). The viscosity of the dispersant (D) is more preferably 20,000 mPa · s or less, and particularly preferably 10,000 mPa · s or less.

The boiling point of the dispersant (D) is preferably 200 ° C. or higher. In this case, since the dispersant (D) is less likely to volatilize from the composition (X), the storage stability of the composition (X) is further improved.

The weight average molecular weight of the dispersant (D) is preferably 200,000 or less. In this case, the dispersant (D) may have a low viscosity. The weight average molecular weight is more preferably 100,000 or less, and even more preferably 50,000 or less. In the present specification, the weight average molecular weight is a polystyrene-equivalent relative weight average molecular weight obtained from the measurement result by gel permeation chromatography.

As a commercially available product of the dispersant (D), for example, the Solsperth series manufactured by Nippon Louvre Resol Co., Ltd., the DISPERBYK series manufactured by Big Chemie Japan Co., Ltd., the Ajinomoto Fine Techno Co., Ltd. Azispar series, and the like can be used.

More specifically, when a dispersant (D1) having two or more adsorbent groups in one molecule is used as the dispersant (D), the following are exemplified.

When the dispersant (D1) contains a two-terminal dispersant, the dispersant may be, for example, a part number SOLSPERSE41000 manufactured by Lubrizol (a two-terminal dispersant having a phosphoric acid group as an adsorbent, acid value 50 mgKOH /). g, amine value 0 mgKOH / g, viscosity 1500 mP · s, boiling point 200 ° C or higher), product number SOLSERSE45000 manufactured by Lubrizol (biterminal dispersant having a phosphoric acid group as an adsorbent, acid value 235 mgKOH / g, amine value 0 mgKOH) / G, viscosity 1500 mP · s, boiling point 200 ° C or higher) and the like can be used.

When the dispersant (D1) contains a comb-type dispersant, as the comb-type dispersant, for example, product number SOLSERSE32000 manufactured by Lubrizol (comb-type dispersant having an amino group as an adsorbent, acid value 15 mgKOH / g, amine value). 31 mgKOH / g, viscosity 14000 mP · s, boiling point 200 ° C or higher), product number SOLSERSE36000 (comb-type dispersant having a phosphate group as an adsorbent, acid value 15 mgKOH / g, amine value 0 mgKOH / g, viscosity 15000 mP) -S, boiling point 200 ° C or higher) can be used.

When the dispersant (D1) contains a side chain terminal dispersant, the side chain terminal dispersant may be, for example, Actflow CBB3098 (side chain terminal dispersant having a carboxyl group as an adsorbing group) manufactured by Soken Kagaku Co., Ltd. , Acid value 98 mgKOH / g, amine value 0 mgKOH / g, viscosity 9000 mPa · s, boiling point 200 ° C or higher), product name Actflow CB3060 manufactured by Soken Kagaku Co., Ltd. 60 mgKOH / g, amine value 0 mgKOH / g, viscosity 1200 mPa · s, boiling point 200 ° C. or higher) and the like can be used.

When the dispersant (D1) contains a super-branched dispersant, the super-branched dispersant may be, for example, a product number DISPERBYK-2152 manufactured by Big Chemie Co., Ltd. (super-branched having a phosphoric acid group protected by a protecting group as an adsorbing group). A type dispersant, acid value 0 mgKOH / g, amine value 0 mgKOH / g, viscosity 20000 mPa · s, boiling point 200 ° C. or higher) and the like can be used. In DISPERBYK-2152, the acid value is not measured because the phosphoric acid group is protected by a protecting group.

The amount of the dispersant (D) in the composition (X) can be set according to the purpose of improving the dispersibility of the phosphor (B) and the light scattering particles (C).

For example, when improving the dispersibility of the fluorescent substance (B), the amount of the dispersant (D) with respect to 100 parts by mass of the fluorescent substance (B) is preferably 5 parts by mass or more and 60 parts by mass or less. When the amount of the dispersant (D) is 5 parts by mass or more, the function of the dispersant (D) can be effectively exhibited, and when the amount is 60 parts by mass or less, the dispersant (D) in the color resist 1 can be effectively exhibited. It is possible to prevent free molecules from inhibiting the adhesion between the color resist 1 and the member made of the inorganic material. Further, the amount of the dispersant (D) is more preferably 15 parts by mass or more, more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. preferable. When the fluorescent substance (B) is subjected to a surface treatment for improving the dispersibility, the fluorescent substance (B) can be used even if the composition (X) does not contain the dispersant (D). May be well dispersed.

When improving the dispersibility of the light-scattering particles (C), the amount (percentage) of the dispersant (D) with respect to the light-scattering particles (C) is preferably 1% by mass or more and 60% by mass or less. When this percentage is 1% by mass or more, the dispersibility of the light-scattering particles (C) can be particularly enhanced. When this percentage is 60% by mass or less, there is an advantage that the unadsorbed dispersant does not exist in the resin and discoloration due to light is unlikely to occur. This percentage is more preferably 3% by mass or more, and further preferably 7% by mass or more. Further, this percentage is more preferably 40% by mass or less, and further preferably 30% by mass or less.

<Other ingredients>
In a preferred embodiment of the present disclosure, it is preferable that the composition (X) does not contain a solvent, or the content of the solvent is 1% by mass or less. Therefore, outgas is less likely to be generated from the composition (X) and the cured product. In addition, the storage stability of the composition (X) is further enhanced.

The composition (X) may further contain a hygroscopic agent (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, so that the cured product And the quantum dot phosphor (B1) in the color resist 1 is less likely to deteriorate. The average particle size of the hygroscopic agent (F) is preferably 200 nm or less. In this case, the cured product can have high transparency.

The hygroscopic agent (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 preferable. The components that can be contained in the hygroscopic agent (F) are not limited to the above. It is particularly preferable that the hygroscopic agent (F) contains zeolite particles.

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

Zeolite particles preferably contain sodium ions, and therefore 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 as a raw material among zeolites containing sodium ions. It is particularly preferable that the zeolite particles are produced using 4A-type zeolite as a raw material among A-type zeolites. In these cases, the zeolite particles have a crystal structure suitable for adsorbing water.

The average particle size of the hygroscopic agent (F) is preferably 10 nm or more and 200 nm or less. When the average particle size is 200 nm or less, the cured product can have particularly high transparency. Further, when the average particle size is 10 nm or more, good hygroscopicity of the hygroscopic agent (F) can be maintained. The average particle size is the median diameter calculated from the measurement result by the dynamic light scattering method, that is, the cumulative 50% diameter (D50). As the measuring device, Nanotrack Nanotrac Wave series manufactured by Microtrack Bell Co., Ltd. can be used.

The average particle size of the hygroscopic agent (F) is more preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 70 nm or less. Further, the average particle size of the hygroscopic agent (F) is preferably 20 nm or more, and 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 hygroscopic agent (F) is preferably 300 nm or less, and more preferably 100 nm or less. In this case, the cured product can have particularly high transparency.

When the composition (X) contains the hygroscopic agent (F), the ratio 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. When the ratio 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 hygroscopic agent (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 can be applied by an inkjet method. You can also. The proportion of the hygroscopic agent (F) is more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The proportion of the hygroscopic agent (F) is more preferably 15% by mass or less, and particularly preferably 13% by mass or less.

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

The color resist 1 produced from the composition (X), the color filter 2 including the color resist 1, and the 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 irradiating the composition (X) with ultraviolet rays to cure it.

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

When the composition (X) has a property of lowering the viscosity by heating, the composition (X) may be heated and then the composition (X) may be applied and molded by an inkjet method. When the viscosity of the composition (X) at 40 ° C. is 30 mPa · s or less, particularly 15 mPa · s or less, the viscosity of the composition (X) can be reduced by slightly heating, and the viscosity is reduced. The composition (X) can be ejected by an inkjet method. The heating temperature of the composition (X) is, for example, 20 ° C. or higher and 50 ° C. or lower.

Further, when the fluorescent substance (B) in the composition (X) absorbs ultraviolet rays when the composition (X) is cured, the reaction efficiency is lowered due to the fluorescent substance (B) absorbing the ultraviolet rays. It is preferable to select the wavelength of the ultraviolet rays to irradiate the composition (X) so that it is unlikely to occur. For example, when a green quantum dot phosphor composed of CdSe / ZnS core-shell type semiconductor particles is used, it is preferable that the wavelength of ultraviolet rays irradiating 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, a transparent resin or glass. A partition wall 3 is formed on one surface of the support substrate 4. The partition wall 3 is made of, for example, a polyimide resin. As a result, a plurality of recesses 14 partitioned by the partition wall 3 are formed on the support substrate 4. Next, the composition (X) is ejected into the recess 14 by an inkjet method. Subsequently, the composition (X) in the recess 14 is cured by irradiating it with ultraviolet rays to prepare a color resist 1.

Next, the protective layer 5 is prepared so as to cover the color resist 1. The protective layer 5 includes, for example, a layer made of a 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 from, for example, silicon nitride or silicon oxide. The protective layer 5 may include either one of the resin layer and the inorganic layer, or may contain 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 may include a plurality of inorganic layers. When the protective layer 5 includes a resin layer and an inorganic layer, in the protective layer 5, the adjacent resin layer and the inorganic layer are arranged in a direction in which the color resist 1 and the protective layer 5 are arranged side by side. For example, the protective layer 5 includes 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 contains 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 vacuum or reduced pressure, but as described above, in the present embodiment, outgas can be less likely to be generated from the color resist 1 under vacuum or reduced pressure. Therefore, even if the color resist 1 is exposed to vacuum or reduced pressure in the manufacturing process of the color filter 2, voids due to outgas can be less likely to occur in the color filter 2.

It is preferable that the step of producing the color resist 1 from the composition (X) does not include a drying step of drying the composition (X) between molding the composition (X) and curing it. The drying step of drying the composition (X) is to remove at least a part 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 improved. In particular, when the composition (X) does not contain a solvent or the content of the solvent is 1% by mass or less, outgas can be less likely to be generated from the color resist 1 without drying the composition (X).

When the composition (X) contains 1% by mass or less of a solvent, the step of producing the color resist 1 from the composition (X) may include a drying step of drying the composition (X), if necessary. In this case, particularly when the solvent content of the composition (X) is 1% by mass or less, the heating temperature of the composition (X) is reduced and the heating time is shortened when the composition (X) is dried. At least one of the transformations can be achieved. For example, the heating temperature can be 120 ° C. or lower, less than 100 ° C., or less than 50 ° C. When the composition (X) is dried, outgas can be further reduced from the color resist 1.

When the manufacturing method of the color filter 2 includes manufacturing the color resist 1 and manufacturing the protective layer 5, this manufacturing method prepares the color resist 1 from the composition (X) and then prepares 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 the present 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 if the color resist 1 is not dried. It can be difficult.

When the composition (X) contains 1% by mass or less of a solvent, if necessary, the method for producing the color filter 2 is from the production of the color resist 1 from the composition (X) to the production of the protective layer 5. In the meantime, a drying step of drying the color resist 1 may be included. In this case, when the solvent content of the composition (X) is 1% by mass or less, at least one of the reduction of the heating temperature and the shortening of the heating time of the color resist 1 when the color resist 1 is dried. Can be realized. For example, the heating temperature can be 120 ° C. or lower, less than 100 ° C., or less than 50 ° C. When the color resist 1 is dried, it is possible to further reduce the generation of outgas from the color resist 1.

The method for producing the color filter 2 includes both a drying step of drying the composition (X) and a drying step of drying the color resist 1 from the molding of the composition (X) to the production of the protective layer 5. It is particularly preferable not to include it. However, when the composition (X) contains 1% by mass or less of a solvent, if necessary, the method for producing the color filter 2 includes a drying step of drying at least one of the composition (X) and the color resist 1. It may be included. Also in this case, as described above, at least one of reduction of the heating temperature for drying and shortening of the heating time can be realized.

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

It should be noted that heating the color resist for a purpose other than drying the color resist 1 after producing the color resist 1 is not included in the drying step of drying the color resist 1. For example, in order to form the above-mentioned inorganic layer on the color resist 1 by a vapor deposition method such as a plasma CVD method, heating the color resist 1 in a chamber under vacuum or reduced pressure is included in the drying step. not.

Next, the light emitting device 11 provided with the color filter 2 will be described. The light emitting device 11 includes, for example, a color filter 2 including a color resist 1 and a light source for irradiating the color filter 2 with light. The light emitting device 11 may be a display device (display) that visually displays information such as an image by light.

The light emitting device 11 shown in FIG. 1A is a display device, and 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 laminated in this order. The light source in the backlight unit 7 is, for example, a cold cathode fluorescent lamp or a light emitting diode.

The color resist 1 of the color filter 2 in the liquid crystal display device 12 is, for example, a color resist 1r that emits red fluorescence (hereinafter, also referred to as red color resist 1r) and a color resist 1 g that emits green fluorescence (hereinafter, green color resist). 1 g) and a resist 1b that does not emit fluorescence (hereinafter, also referred to as a 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 red color resist 1r contain a quantum dot phosphor (B1) that emits red fluorescence. 1 g of the green color resist and the composition (X) for producing the green color resist contain a quantum dot phosphor (B1) that emits green fluorescence. The composition for producing the transparent resist 1b may be a transparent cured product, but has, for example, a composition obtained by removing the phosphor (B) from the composition (X).

The fluorescent color emitted by the color resist 1 and the fluorescent color emitted by the quantum dot phosphor (B1) in the color filter 2 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 a blue color resist) instead of the transparent resist 1b. The blue color resist and the composition (X) for producing the blue color resist contain a quantum dot phosphor (B1) 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 superimposed on the liquid crystal panel 6. The color filter 2 may be produced by stacking the support substrate 4 on the liquid crystal panel 6 and then forming the partition wall 3, the color resist 1 and the protective layer 5 on the support substrate 4 by the above method. The color filter 2 may be produced by directly producing the partition wall 3, the color resist 1, and the protective layer 5 on the liquid crystal panel 6 by the above method.

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

The light emitting device 11 shown in FIG. 1B is a display device, and 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 electroluminescence element).

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 that covers the light emitting diodes 9. The protective layer 15 in the light emitting unit 8 includes either one of the resin layer and the inorganic layer, or includes both the resin layer and the inorganic layer, like the protective layer 5 in the color filter 2, for example.

The color resist 1 of the color filter 2 in the LED display device 13 includes, for example, a red color resist 1r, a green color resist 1 g, 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 irradiates the paired color resist 1, whereby fluorescence is emitted from the color resist 1. 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. Includes blue light passing through the transparent resist 1b. Therefore, full-color display using the three primary colors is possible.

When the light emitting diode 9 emits white light, a blue color resist that emits blue fluorescence may be contained instead of the transparent resist 1b. In this case, the light emitting diode 9 is paired with 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 blue color resist. It may include a light emitting diode (third light emitting diode). In other words, the light emitting diode 9 includes a first light emitting diode that irradiates the red color resist 1r with light, a second light emitting diode that irradiates the green color resist 1 g with light, and a third light emitting diode that irradiates the blue color resist with light. And may be included. 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. 1. Preparation of Composition The compositions of Examples and Comparative Examples were prepared by mixing the components shown in the table below. In the table, the blending amount of the components other than the light scattering particles is shown by the mass part, and the blending amount of the light scattering particles is shown by the volume percentage based on the entire composition.

Among the components shown in the table, the details of the components other than the light-scattering particles are as follows. The viscosities of the following components are measured using a rheometer (manufactured by Anton Paar Japan Co., Ltd., model number DHR-2) under the conditions of a temperature of 25 ° C. and a shear rate of 1000 s ^-1 .

<Reaction curable compound>
-Acryloyl morpholine: Boiling point 265 ° C., viscosity 12 mPa · s.
-Dipropylene glycol diacrylate: Boiling point 120 ° C., viscosity 10 mPa · s.
-Triethylene glycol dimethacrylate: Boiling point 290 ° C. Viscosity 8 mPa · s.
-1,9-Nonanediol diacrylate: Boiling point 342 ° C. Viscosity 8 mPa · s.
-Pentaerythritol tetraacrylate: boiling point 450 ° C., viscosity 350 mPa · s.

<Photopolymerization initiator>
-Irgacure 907: BASF, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.
-Irgacure TPO: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide manufactured by BASF.

<Quantum dot phosphor>
-Green quantum dot phosphor: CdSe / ZnS core-shell type semiconductor particle, median diameter 3.3 nm, manufactured by SIGMA-ALDRICH, product name CdSe / ZnS530.
-Red quantum dot phosphor: CdSe / ZnS core-shell type semiconductor particles, median-based 5.2 nm, manufactured by SIGMA-ALDRICH, product name CdSe / ZnS610.

<Dispersant>
-CBB3098: Side chain terminal dispersant having a carboxyl group as an adsorbent, acid value 98 mgKOH / g, viscosity 9000 mP · s, weight average molecular weight 3000, manufactured by Soken Kagaku, product number CBB3098.
-DISPERBYK-2155: Polyurethane structure dispersant having a plurality of tertiary amino groups as adsorbents in one molecule, amine value 48 mgKOH / g, viscosity 13000 mP · s, weight average molecular weight 20000, manufactured by Big Chemie, product number DISPERBYK- 2155.

The details of the light-scattering particles among the components shown in the table are as follows. The refractive index of the hollow particles is the refractive index of the portion of the hollow particles other than the hollow portion.

Tables 1 and 2 show the details of the light-scattering particles used in Example A and Comparative Example A. In addition, Example A is an Example corresponding to the first embodiment.

Table 3 shows the details of the light-scattering particles used in Example B and Comparative Example B. In addition, Example B is an Example corresponding to the second embodiment.

2. 2. Measurement of Refractive Index of Cured Product of Reaction Curable Compound A coating film is prepared by applying a composition obtained by mixing only a photocurable compound and a photopolymerizable compound in each Example and Comparative Example. A film having a thickness of 300 μm is obtained by irradiating the coating film with ultraviolet rays for 20 seconds under the condition of 500 mW / cm ² using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus in an atmospheric atmosphere. Was produced. The refractive index of this sample was measured with respect to light having a wavelength of 589 nm at 25 ° C. using a multi-wavelength Abbe refractometer DR-M4 manufactured by Atago.

3. 3. Evaluation test The following evaluation test was carried out for Examples and Comparative Examples. The results of Example A and Comparative Example A are shown in Tables 4 to 6. The results of Example B and Comparative Example B are shown in Tables 7 and 8.

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

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

(3) Inkjet property The composition is placed in a cartridge of an inkjet printer (manufactured by Ricoh, type 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. The test pattern was printed continuously. As a result, "A" indicates that the composition can be discharged for 1 hour and the discharge operation is stable, and "B" indicates that the composition can be discharged for 1 hour but the discharge operation becomes intermittently unstable. The case where the nozzle was clogged and the composition could not be discharged 1 hour before the start of discharge was evaluated as "C".

(4) Precipitation stability The following tests were carried out on the composition. When the composition was placed in a transparent dedicated test container with a capacity of 20 cm ³ to a height of 41 mm and the composition was irradiated with light having a wavelength of 880 nm using the Turbiscan Lab, a high-performance dispersion stability evaluation device manufactured by Sanyo Trading Co., Ltd. , The peak of the scattering intensity of the composition was measured in the portion within 3 mm in height from the bottom of the test container (initial value). Subsequently, the test container containing the composition was allowed to stand in a high temperature bath at 40 ° C. for 14 days, and then the same test was performed.

In the evaluation, "A" is when the increase in the peak of the scattering intensity is 1% or less of the initial value, "B" is when the increase in the peak of the scattering intensity is more than 1% and 3% or less of the initial value, and the scattering intensity is The case where the increase in the peak was more than 3% and 5% or less of the initial value was evaluated as "C", and the case where the increase in the peak of the scattering intensity was more than 5% of the initial value was evaluated as "D". In the case of "D", the sedimentation was not eliminated even if the composition was lightly shaken in the test container.

(5) Evaluation of light scattering The following tests were conducted on the composition. The composition was applied onto quartz glass having a thickness of 1 mm to prepare a coating film. This coating film is irradiated with ultraviolet rays under the condition of 500 mW / cm ² for 3 seconds (integrated light amount 1500 mJ / cm ² ) using an LED-UV irradiator (peak wavelength 385 nm) manufactured by Panasonic Electric Works Sunkus in an atmospheric atmosphere. , The coating film was cured. As a result, a film having a thickness of 10 μm was produced on quartz glass. The transmittance of light at a wavelength of 450 nm of this film was measured. A spectrophotometer (U-4100 manufactured by Hitachi, Ltd.) was used for the measurement.

As a result, the case where the transmittance is 60% or less is evaluated as "A", the case where the transmittance is higher than 60% and 75% or less is evaluated as "B", and the case where the transmittance is higher than 75% is evaluated as "C". bottom.

Claims

Reaction curable compound (A),
Containing a phosphor (B) and a light scattering particle (C),
The light scattering particles (C) include core-shell type particles (C0) having a core portion and a shell covering the core portion.
The specific gravity of the core portion is 2.0 or less, and the core portion has a specific gravity of 2.0 or less.
The refractive index of the shell is 1.9 or more.
Composition for forming a wavelength conversion member.
The core portion contains organic resin particles.
The composition for molding a wavelength conversion member according to claim 1.
The core portion contains hollow particles.
The composition for forming a wavelength conversion member according to claim 1 or 2.
The core portion includes a hollow portion.
The composition for forming a wavelength conversion member according to any one of claims 1 to 3.
The average particle size of the core-shell type particles (C0) is 50 nm or more and 3000 nm or less.
The composition for forming a wavelength conversion member according to any one of claims 1 to 4.
The thickness of the shell is 5 nm or more and 60 nm or less.
The composition for forming a wavelength conversion member according to any one of claims 1 to 5.
The percentage of the core-shell type particles (C0) to the solid content in the composition for forming a wavelength conversion member is 1% by volume or more and 20% by volume or less.
The composition for forming a wavelength conversion member according to any one of claims 1 to 6.
Reaction curable compound (A),
Containing a phosphor (B) and a light scattering particle (C),
The light scattering particles (C) contain titanium oxide particles (C1) and hollow particles (C2).
Composition for forming a wavelength conversion member.
The average particle size of the titanium oxide particles (C1) is 300 nm or less.
The composition for molding a wavelength conversion member according to claim 8.
The percentage of the titanium oxide particles (C1) to the solid content in the composition for forming a wavelength conversion member is 1% by volume or more and 20% by volume or less.
The composition for forming a wavelength conversion member according to claim 8 or 9.
The hollow particles (C2) contain hollow resin particles (C21), and the hollow particles (C2) contain hollow resin particles (C21).
The average particle size of the hollow resin particles (C21) is 1.5 times or more the average particle size of the titanium oxide particles (C1).
The composition for forming a wavelength conversion member according to any one of claims 8 to 10.
The hollow particles (C2) contain hollow inorganic particles (C22), and the hollow particles (C2) contain hollow inorganic particles (C22).
The average particle size of the hollow inorganic particles (C22) is 220 nm or more, and is twice or more the average particle size of the titanium oxide particles (C1).
The composition for forming a wavelength conversion member according to any one of claims 8 to 11.
The percentage of the hollow particles (C2) to the solid content in the composition for forming a wavelength conversion member is 0.1% by volume or more and 20% by volume or less.
The composition for forming a wavelength conversion member according to any one of claims 8 to 12.
Further containing the dispersant (D),
The composition for forming a wavelength conversion member according to any one of claims 1 to 13.
Further containing the dispersant (D),
The dispersant (D) contains a dispersant (D1) having two or more adsorbent groups in one molecule.
The composition for forming a wavelength conversion member according to any one of claims 8 to 13.
The reaction-curable compound (A) contains a photocurable compound.
The composition for forming a wavelength conversion member according to any one of claims 1 to 15.
The fluorophore (B) contains a quantum dot fluorophore (B1).
The composition for forming a wavelength conversion member according to any one of claims 1 to 16.
Satisfying at least one of the viscosity at 25 ° C. being 30 mPa · s or less and the viscosity at 40 ° C. being 30 mPa · s or less.
The composition for forming a wavelength conversion member according to any one of claims 1 to 17.
A cured product of the composition for forming a wavelength conversion member according to any one of claims 1 to 18.
Color resist.
19. The color resist according to claim 19.
Color filter.
The color filter according to claim 20 and a light source for irradiating the color filter with light.
Light emitting device.
It is a display device,
The light emitting device according to claim 21.
The composition for molding a wavelength conversion member according to any one of claims 1 to 18 is molded by an inkjet method, and then the composition for molding a wavelength conversion member is irradiated with ultraviolet rays to be cured.
A method for manufacturing a color resist.
It is a method of manufacturing a light emitting device including a color filter including a color resist and a light source for irradiating the color filter with light.
23. The color resist is produced by the method according to claim 23.
Manufacturing method of light emitting device.