WO2022186034A1

WO2022186034A1 - Resin composition for cutting off blue light using hollow metal oxide particles, and use thereof

Info

Publication number: WO2022186034A1
Application number: PCT/JP2022/007544
Authority: WO
Inventors: 幸広原; 透栗橋; 誠古江; 慧史西川
Original assignee: 日本化薬株式会社
Priority date: 2021-03-01
Filing date: 2022-02-24
Publication date: 2022-09-09
Also published as: TW202302743A

Abstract

This resin composition for cutting off blue light contains (A) hollow metal oxide particles, and (B) a transparent resin, wherein in (A), when a hollow diameter is A (nm), and a particle diameter is B (nm), A and B satisfy the following expressions (1) and (2).　(1): 0.65≤A/B≤0.9 (2): 100 nm≤B≤250 nm

Description

Resin composition for cutting blue light using metal oxide hollow particles and use thereof

The present invention relates to a resin composition containing metal oxide hollow particles and a transparent resin, and uses thereof. More specifically, the present invention relates to a resin composition that has an optical property of being able to selectively scatter a specific wavelength and is particularly excellent in cutting blue light, and uses thereof.

Hollow particles are widely used as microcapsules containing various functional substances inside the particles. In the fields of coatings, inks and paints, cosmetics, etc., it is also known to be useful as a light scattering agent and a light scattering aid for imparting performance such as brightness, gloss, opacity, and whiteness. Furthermore, since the inside is void, effects as a refractive index adjuster, a permittivity adjuster, a lightening agent, a sound insulating material, and a heat insulating material can be expected.
Among hollow particles, hollow particles of metal oxides such as silica, titanium oxide and zirconium oxide are industrially useful because they are excellent in structural stability and chemical stability. In particular, hollow particles containing titanium oxide are considered useful as light scattering materials and catalyst materials because of their high refractive index and catalytic activity.

Several methods have been proposed as methods for producing such metal oxide hollow particles. Patent Document 1 proposes a method of preparing core-shell type particles by using resin particles as template particles and forming a layer of titanium oxide on the surface of the resin particles, and removing the resin particles. However, this method has a problem that the core-shell particles are fused to each other or the hollow structure is destroyed when the resin particles are removed by baking.

Further, in Patent Document 2, an inorganic compound aqueous solution is mixed and emulsified with an organic solvent using a surfactant to prepare a water-in-oil emulsion, and this is mixed with another aqueous solution to cause a precipitation reaction at the water droplet interface. A method has been proposed for producing hollow particles by allowing However, this method has a problem that the particle size distribution of the hollow particles is wide and the reproducibility of strength and particle size is not good.

In Patent Document 3, resin particles and inorganic particles smaller than the resin particles are stirred at high speed in an air current to coat the resin particles with the inorganic particles to prepare composite particles, and then the composite particles are heated. A method has been proposed for producing hollow particles by decomposing resin particles. However, the hollow particles produced by this method have a problem that the particle diameter is large and the strength is weak.

Japanese Patent Application Laid-Open No. 2013-23676 Japanese Patent Laid-Open No. 06-330606 Japanese Patent Laid-Open No. 05-138009

A resin composition using conventional hollow particles as described above has a short pot life due to the influence of sedimentation, which may cause defects during the manufacturing process. In addition, the optical properties are not sufficient, and in particular, wavelengths other than the desired wavelength are scattered, making it difficult to develop various applications.

As a result of intensive studies, the present inventors have found that a resin composition using hollow particles having specific properties and a transparent resin can selectively scatter unique optical properties, specifically blue light.
That is, the present invention relates to the following 1) to 10).
1)
(A) metal oxide hollow particles, and (B) a resin composition for cutting blue light containing a transparent resin,
A resin composition for cutting blue light, wherein A and B satisfy the following formulas (1) and (2), where A (nm) is the hollow diameter and B (nm) is the particle diameter of (A).

0.65≦A/B≦0.9 (1)
100 nm ≤ B ≤ 250 nm (2)

2)
When X (%) is the minimum transmittance at a wavelength of 400 nm to 500 nm and Y (%) is the transmittance at 600 nm when measured as a film with a thickness of 5 μm, X and Y are represented by the following formulas (3) and ( The resin composition for cutting blue light according to 1) above, which satisfies 4).

0%≦X≦60% (3)
0.25≦X/Y≦0.8 (4)

3)
The resin composition for cutting blue light according to 1) or 2) above, wherein the (A) metal oxide hollow particles are (A-1) hollow particles containing rutile-type titanium oxide.
4)
The blue light cut according to any one of claims 1 to 3, wherein the (A) metal oxide hollow particles are hollow particles containing (A-1) rutile-type titanium oxide and (A-2) silica. resin composition for
5)
4) above, wherein the content of (A-2) silica in (A) is 0.5% by mass or more and 30% by mass or less.
6)
The resin composition for cutting blue light according to any one of 1) to 5) above, wherein the (B) transparent resin is a curable resin.
7)
A blue light blocking film comprising the blue light blocking resin composition according to any one of 1) to 6) above.
8)
A blue light blocking layer comprising the blue light blocking resin composition according to any one of 1) to 6) above.
9)
An optical filter having the blue light cut film described in 7) above or the blue light cut layer described in 8) above.
10)
An eyewear comprising the blue light cut film described in 7) above or the blue light cut layer described in 8) above.

According to the present invention, it is possible to provide resin compositions and films that are excellent in the selective light scattering properties of specific wavelengths, so it is particularly useful for developing applications for cutting blue light.

FIG. 1 is a diagram showing an SEM image and EDS data of hollow structure particles according to Example 1. FIG.

In this specification, the resin composition for cutting blue light may be simply referred to as a resin composition. Also, "~" shall be included before and after the numerical value.
[(A) Metal oxide hollow particles]
The resin composition of the present invention contains metal oxide hollow particles as component (A).
Metal oxides include, for example, zinc oxide, titanium oxide, cerium oxide, zirconium oxide, iron oxide, silica, and the like, and these can be used singly or in combination of two or more. Among these fine particle metal oxides, zinc oxide and titanium oxide are preferred, and titanium oxide is more preferred.
These metal oxides may be surface-treated with oxides and/or hydroxides of aluminum, silica, silicon oxides and/or hydroxides. Alternatively, these metal oxides are one or two of fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc. It may have been surface treated with more than one seed.
In addition, the hollow particles are spherical, approximately spherical, uneven, or irregularly shaped particles having holes formed therein and having a shell made of the metal oxide described above, and are preferably spherical or approximately spherical. , more preferably spherical. Moreover, it is preferable that the holes inside the hollow particles have a high degree of circularity when the holes are regarded as spheres.
In this specification, metal oxide hollow particles may be simply referred to as hollow particles, and rutile-type titanium oxide may be simply referred to as titanium oxide.

[(A-1) Rutile-type titanium oxide hollow particles]
The metal oxide hollow particles (A) are most preferably titanium oxide, and the titanium oxide is particularly preferably of the rutile type.
(A-1) Rutile-type titanium oxide is excellent in that it has a low photocatalytic function and a high refractive index, so that the reflectance with respect to wavelength can be controlled. The proportion of rutile-type titanium oxide in titanium oxide is generally 80% to 100% by mass, preferably 85% to 100% by mass, more preferably 90% to 100% by mass. The ratio is a value calculated from the X-ray diffraction peak.
It can be confirmed by a known method that the titanium oxide constituting the hollow particles according to the present embodiment is a single crystal. Known methods include, for example, a method of measuring electron diffraction images of single particles using a transmission electron microscope (TEM). As used herein, the term "single crystal" means that the electron diffraction image of a single particle is a spot image.

[(A-2) silica]
The (A) metal oxide hollow particles used in the resin composition of the present invention preferably contain (A-2) silica in the shell portion. The silica may be crystalline or amorphous, preferably amorphous. It can be confirmed by a known method that silica is amorphous. Known methods include, for example, a method of measuring diffraction peaks derived from silica crystals (eg, α-SiO ₂ ) using an X-ray diffractometer or the like. As used herein, the term "amorphous" means that no distinct diffraction peaks derived from crystals appear.
Further, when (A-1) rutile-type titanium oxide contains silica, the content of titanium oxide in (A) metal oxide hollow particles is 70.0% by mass or more and 99.5% by mass or less. preferable. More preferred upper limits for the content of titanium oxide are 98.5% by mass, 97.5% by mass, 96.5% by mass and 95.5% by mass, and particularly preferably 95.0% by mass. . More preferable lower limits are 75.0% by mass, 80.0% by mass, 85.0% by mass, 86.0% by mass, 87.0% by mass, 88.0% by mass, and 89.0% by mass. Yes, particularly preferably 90.0% by mass. Therefore, the content of titanium oxide is most preferably 90.0% by mass or more and 95.0% by mass or less.
Further, the hollow particles according to the present embodiment preferably have a silica content of 0.5% by mass or more and 30.0% by mass or less. More preferred upper limits for the silica content are 25.0% by mass, 20.0% by mass, 15.0% by mass, 14.0% by mass, 13.0% by mass, 12.0% by mass, and 11.0% by mass. 0% by mass, particularly preferably 10.0% by mass. More preferable lower limits are 1.5% by mass, 2.0% by mass, 2.2% by mass, 2.5% by mass, 3.5% by mass and 4.5% by mass, and particularly preferably 5% by mass. .0% by mass. Therefore, the content of silica is most preferably 5.0% by mass or more and 10.0% by mass.
The content of titanium oxide and silica contained in the hollow particles is calculated assuming that the titanium oxide precursor and silica precursor in the production of the hollow particles are converted to titanium oxide and silica at a conversion rate of 100%. When calculating these percentages, round off to the second decimal place and enter the first decimal place.
In the hollow particles, the boundary between the titanium oxide layer having a hollow structure and the silica layer may be a composite oxide. When silica is within this range, it is possible to efficiently shield light with a wavelength of 400 to 500 nm, which is blue light, and reduce the transmittance.

[Hollow diameter and particle diameter parameters A/B]
In the metal oxide hollow particles used in the resin composition of the present invention, when the hollow diameter of the hollow particles is A (nm) and the particle diameter of the hollow particles is B (nm), A/B is the above formula (1) is characterized by satisfying That is, the value of A/B is 0.65-0.90. Preferred lower limits of A/B are 0.68, 0.70 and 0.75 in order, and particularly preferably 0.77. Moreover, the upper limit values are 0.88 and 0.85 in the order of preference, and particularly preferably 0.80. That is, the most preferable range of A/B is 0.77 to 0.80. If the thickness of the shell is too thin, the hollow structure may collapse during mixing.
It should be noted that the hollow particles according to this embodiment preferably do not have pores leading from the surface of the particles to the internal pores. Whether or not it has such pores can be determined, for example, by using a pore distribution measuring device (eg, BELSORP-mini II manufactured by Microtrack Bell Co., Ltd.) to measure the amount of adsorption and desorption with respect to relative pressure. can be confirmed by As used herein, "having no pores leading to internal pores" means that the adsorption-desorption isotherm created from the adsorption and desorption amounts is not type IV or type V in the IUPAC classification. . Within the IUPAC classification, Types II and III are preferred, with Type II being more preferred.
The hollow diameter A of the hollow particles and the primary particle diameter B of the hollow particles are the hollow diameter A of the hollow structure of 10 hollow structure particles randomly photographed with a transmission electron microscope (TEM), and the primary particles of the hollow particles. It is the arithmetic mean value of the diameter B. When the effective figure of the ratio A/B is one decimal place, it is calculated by rounding off the second decimal place. When the effective digits of the ratio A/B are two digits after the decimal point, the third digit after the decimal point is rounded off.
In this specification, the hollow diameter of the hollow particles may be expressed as the inner diameter.

[Primary particle diameter of hollow particles]
The primary particle diameter of the metal oxide hollow particles used in the resin composition of the present invention is characterized by satisfying the above formula (2) when expressed in B (nm). That is, the (A) metal oxide hollow particles have a primary particle diameter of 100 nm or more and 250 nm or less. More preferable upper limits of B are 240 nm, 235 nm, 230 nm, 225 nm, 220 nm and 215 nm, and particularly preferably 210 nm. More preferred values for the lower limit are 120 nm, 140 nm, 150 nm, 160 nm, 170 nm and 180 nm, and particularly preferably 190 nm. That is, the range of B is most preferably 190 nm or more and 210 nm or less.

[Transmittance X (%) of resin composition for cutting blue light]
If the minimum transmittance at a wavelength of 400 nm to 500 nm of a film (film) formed to a thickness of 5 μm by coating the resin composition of the present invention is X (%), it preferably satisfies the above formula (3). Preferred upper limits of the transmittance X are 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, and may be 0% in order. If the transmittance is too high, blue light cannot be blocked, so the lower the transmittance at the wavelength, the better.
In addition, film formation is usually carried out through coating, drying, and curing steps of a resin composition. The coating step is a step of coating with a spin coater or the like, and the coating is performed under optimum conditions such as the concentration of the solvent in the resin composition to give a film thickness of 5 μm after film formation. The drying step is a step of drying the solvent using a hot plate or the like, and is performed under optimum conditions based on the type and amount of the solvent. In addition, the drying process is unnecessary for a resin composition containing no solvent. The curing step is a step of curing a curable resin, and photocuring, heat curing, or a combination thereof is used depending on the composition of the resin. However, when the resin used in the resin composition is only a thermoplastic resin, the curing step is unnecessary. Although the film is formed so as to have a film thickness of 5 μm after film formation, it is not strictly necessary to have a film thickness of 5 μm.
The transmittance can be measured using a spectrophotometer, specifically, using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation).

[Transmittance parameter X/Y]
Assuming that the transmittance at a wavelength of 600 nm of a film formed by applying the resin composition of the present invention to a thickness of 5 μm is Y (%), the above formula (4) is preferably satisfied. This means that the transmittance in the blue light region is suppressed to 1/4 to 4/5 of the transmittance of 600 nm where visibility is high. Preferred lower limit values of X/Y are 0.26, 0.28 and 0.30 in order, and preferred upper limit values are 0.78, 0.76, 0.75, 0.70 and 0.68 in order. 0.67, 0.66, 0.65, 0.64, 0.56, 0.55, 0.54, 0.52, 0.51, 0.50, 0.47, 0.46; 0.45 is particularly preferred. That is, the most preferable range of X/Y is 0.30 or more and 0.45 or less.

<Coefficient of variation of primary particle size>
The (A) metal oxide hollow particles used in the resin composition of the present invention preferably have a coefficient of variation of primary particles of 10% or less.
The variation coefficient of the primary particle diameter of the hollow particles can be calculated from the following formula.
Variation coefficient (%) = standard deviation of primary particle size (nm) / arithmetic mean particle size (nm)
A smaller coefficient of variation is preferable because it indicates that particles of uniform size are obtained. The coefficient of variation is usually 10% or less, preferably 8% or less, more preferably 7% or less, still more preferably 5% or less. The lower limit is preferably as small as possible, ideally 0%.

<Sphericality>
The (A) metal oxide hollow particles used in the resin composition of the present invention preferably have a sphericity of 0.5 or more and 1.0 or less.
Sphericity can be measured by a transmission electron microscope (TEM). That is, it is an arithmetic mean value calculated using the following formula from the long axes and areas of ten hollow particles photographed at random. When the sphericity has only one significant figure after the decimal point, it is calculated by rounding off the second decimal place. When the sphericity has two significant digits below the decimal point, it is calculated by rounding off to the third decimal place.
Sphericality = (4 x particle area (nm ² ))/(π x (major axis (nm)) ² )
Also, the sphericity may be calculated using image analysis software Image J.
When the sphericity is within the above range, the dispersibility is improved and the reflectance control at wavelength is excellent.

<Other Configurations of Hollow Particles>
The (A) metal oxide hollow particles used in the resin composition of the present invention include, in addition to metal oxides, the silica described above, and further, for example, Sn, Cd, Fe, Ni, Zn, Mn, Co, Cr, An element selected from Cu, K, Na, Li, P, S and the like may be contained. These elements may be of one type or two or more types.

When the (A) metal oxide hollow particles used in the resin composition of the present invention further contain elements other than titanium oxide and silica, the total content of these elements is equal to the number of moles of titanium in the titanium oxide. On the other hand, it is usually 0.1% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass. Such a range tends to make it easier to obtain hollow particles with little coloration.

The metal oxide hollow particles used in the resin composition of the present invention may, if necessary, further have a layer of other substances on their surfaces. Other substances include, for example, alumina, aluminum hydroxide, zinc oxide, zinc hydroxide, zirconia, organic substances, and the like.

<Method for producing hollow particles>
Metal oxide hollow particles used in the resin composition of the present invention are described, for example, in Xiong Wen (David) Lou, Lynden A.; Archer and Zichao Yang, Adv. Mater. , 2008, 20, 3987-4019 and the like. However, it is not limited to this manufacturing method. Note that the following description is given as an example in which titanium oxide is used as the metal oxide.

In particular, a step of forming a shell containing a titanium oxide precursor and a silica precursor on the surface of a template particle serving as a core to obtain a core/shell particle (hereinafter also referred to as “first step”); A step of removing the template particles from the particles to obtain shell particles (hereinafter also referred to as a “second step”) and a step of firing the shell particles in an air atmosphere to obtain hollow particles (hereinafter referred to as a “third step”). Also called.) and a manufacturing method including.

Unless otherwise specified, each step described below is preferably carried out under stirring.

<First step>
The first step includes a step of reacting template particles with a titanium oxide precursor and a silica precursor in an organic solvent in the presence of a base. The silica precursor may be added after adding the titanium oxide precursor, or may be added simultaneously with the titanium oxide precursor. Through the first step, it is possible to obtain core/shell particles in which a shell containing a titanium oxide precursor and a silica precursor is formed on the surface of a template particle serving as a core.

Template particles include particles selected from polymeric particles and inorganic particles. Specific examples thereof include polymer particles obtained by polymerizing at least one type of monomer selected from (meth)acrylate, vinyl, styrene, and urethane; calcium carbonate, iron oxide, cobalt oxide, inorganic particles such as manganese oxide, chromium oxide, and nickel oxide; Among these, polymer particles are preferred, polymer particles containing styrene as a constituent monomer are more preferred, styrene-(meth)acrylic acid polymer particles are still more preferred, and styrene-methacrylic acid polymer particles are particularly preferred.
In this specification, "(meth)acrylate" means both acrylate and methacrylate, and "(meth)acrylic acid" means both acrylic acid and methacrylic acid.

The titanium oxide precursor is not particularly limited as long as it can be converted into titanium oxide by a chemical or physical method. Among the titanium oxide precursors, titanium alkoxides are preferred. Titanium alkoxide is preferably titanium tetraalkoxide, more preferably titanium tetra-C1-C6 alkoxide, and still more preferably titanium tetrabutoxide.

By controlling the amount of titanium oxide precursor added, the thickness of the shell can be controlled. The titanium oxide precursor may be added at once or in several batches in an amount necessary for the shell to have a specific thickness. By adding the titanium oxide precursor in several batches, the thickness of the shell tends to be more uniform.

The silica precursor is not particularly limited as long as it can be converted into silica by a chemical or physical method. Among silica precursors, silane alkoxides are preferred. The silane alkoxide is preferably silane tetraalkoxide, more preferably silane tetra C1-C4 alkoxide, and still more preferably silane tetraethoxide.

Examples of organic solvents include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, butanol, t-butanol, benzyl alcohol, etc.), ketone solvents, Solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetylacetone, etc.), ester solvents (ethyl acetate, methyl acetate, butyl acetate, cellosolve acetate, amyl acetate, etc.), ether solvents (isopropyl ether, methyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4-dioxane, etc.), glycol solvents (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, octylene glycol, etc.), glycol ether solvents (diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), Glycol ester solvents (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), glyme solvents (monoglyme, diglyme, etc.), halogen solvents (dichloromethane, chloroform, etc.), amide solvents (N , N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone), pyridine, sulfolane, acetonitrile, dimethylsulfoxide and the like.

One type of organic solvent may be used alone, or two or more types may be used in combination. By using two or more kinds of organic solvents in combination and controlling the ratio thereof, the concentration of the template particles, the method of adding the base, etc., the first step can be performed while maintaining a good dispersion state of the reaction solution.

Examples of bases include inorganic bases and organic bases. Examples of inorganic bases include hydroxides of Group 1 or Group 2 elements of the periodic table, preferably hydroxides of Na, K, Ca, Mg, Al, Fe and the like; ammonia; and the like. Examples of organic bases include heteroaromatic ring compounds such as pyridine; alkylamines such as triethylamine (preferably trialkylamines, more preferably triC1-C4 alkylamines); hydroxyalkylamines such as triethanolamine (preferably trialkylamines). (hydroxyalkyl)amine, more preferably tri(hydroxy C1-C4 alkylamine)); and the like.

The first step is preferably performed under an inert gas atmosphere such as nitrogen or argon.
The reaction temperature in the first step is usually -30°C to 80°C, preferably 0°C to 50°C.
Since the reaction time of the first step varies depending on the reaction temperature, shell thickness, etc., it is difficult to determine it unconditionally. As a standard, it is usually 0.1 hour to 10 hours, preferably about 0.5 hour to 7 hours.

When the template particles are polymer particles and the surface potential thereof has the same sign as that of titanium oxide, core/shell particles can also be formed by the following method.
That is, an organic polymer (for example, polyethylenimine, etc.) having a sign opposite to the above surface potential is adsorbed onto the surface of the template particles. The core/shell particles can then be formed by depositing or adsorbing fine particles of titanium oxide onto the surface of the organic polymer and optionally adding a titanium oxide precursor. By using, for example, rutile-type titanium oxide as the fine particles of titanium oxide, the crystal type of titanium oxide produced from the titanium oxide precursor can be rutile-type.

In the first step, the reaction is carried out in the state of dispersion. Therefore, in order to improve the dispersion stability of the dispersion, the first step is preferably carried out in the presence of a dispersant. The type of dispersant is not particularly limited as long as it does not interfere with shell formation. Examples of such dispersants include polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyvinylpyrrolidone; Floren series manufactured by Kyoeisha Chemical Co., Ltd.; DISPERBYK series manufactured by BYK-Chemie Japan; Solspers series; Ajinomoto Fine-Techno Co., Inc. Ajisper series; Kusumoto Kasei Co., Ltd. Disparlon series;

<Second step>
The second step includes a step of dissolving and removing the template particles with a solvent. As such a solvent, a solvent that does not dissolve or destroy the shell particles is preferred. When the template particles are polymer particles, the solvent used in the second step includes organic solvents such as methyl ethyl ketone, toluene, tetrahydrofuran and chloroform. When the template particles are inorganic particles, examples of the solvent used in the second step include aqueous solutions of acids such as dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid.

<Third step>
The third step includes a step of obtaining hollow particles by firing the shell particles obtained in the second step. Generally, the firing can be performed in an atmosphere of a gas selected from one or more of air, nitrogen, argon, hydrogen, ammonia, etc. However, in order to obtain single crystal titanium oxide, the firing must be performed in an air atmosphere. preferably. In this specification, the term “air” refers to the gas that constitutes the lowest layer of the earth's atmosphere and is obtained in the normal environment in which humans live.

The sintering temperature in the third step varies depending on the material of the hollow particles and the like, so it is difficult to generalize. As a guideline, the temperature is usually 600°C to 1500°C or less, preferably 650°C to 1400°C, more preferably 700°C to 1300°C, and still more preferably about 750°C to 1200°C.
Since the firing time in the third step varies depending on the firing temperature and the like, it is difficult to determine indiscriminately. As a guideline, it is usually 0.5 hours to several tens of hours, preferably about 1 hour to 10 hours.

It should be noted that when the template particles are polymer particles, the above second step becomes unnecessary. That is, by the third step of firing the core/shell particles obtained in the first step, removal of the template particles and firing of the shell particles can be performed at the same time. Therefore, the hollow particles can be produced by only two steps, ie, the first step and the third step.

The hollow particles obtained in the third step may contain by-product particles with non-uniform shapes. The proportion of by-product particles is usually 10% or less, preferably 5% or less. Generation of by-product particles can be suppressed by, for example, precisely controlling the synthesis conditions. The content of by-products can be calculated from the number of non-uniformly shaped particles among 100 hollow particles randomly photographed with a transmission electron microscope (TEM) or scanning electron microscope (SEM). can.

[(B) Transparent resin]
The resin composition of the present invention contains (A) metal oxide hollow particles and (B) a transparent resin.
As used herein, the term "transparent resin" means a resin having a degree of transmittance that can be used as eyewear, specifically a resin having a visible transmittance of 20% or more at a wavelength of 380 nm to 780 nm. The visible light transmittance is a value calculated by a method based on JIS R 3106/ISO 9050.
The transparent resin may be a thermoplastic resin or a curable resin (by light and/or heat), preferably a curable resin, particularly preferably a photocurable resin.

<(B-1) Thermoplastic resin>
Thermoplastic resins include high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ultra-low-density polyethylene resin, polypropylene resin, polybutadiene resin, cyclic olefin resin, polymethylpentene resin, polystyrene resin, and ethylene acetate. Vinyl copolymer, ionomer resin, ethylene vinyl alcohol copolymer resin, ethylene ethyl acrylate copolymer, acrylonitrile/styrene resin, acrylonitrile/chlorinated polystyrene/styrene copolymer resin, acrylonitrile/acrylic rubber/styrene copolymer resin, acrylonitrile/butadiene・Styrene copolymer resin, acrylonitrile/EPDM/styrene copolymer resin, silicone rubber/acrylonitrile/styrene copolymer resin, cellulose acetate/butyrate resin, cellulose acetate resin, methacrylic resin, ethylene/methyl methacrylate copolymer resin, ethylene/ethyl acrylate Resin, vinyl chloride resin, chlorinated polyethylene resin, polytetrafluoroethylene resin, tetrafluoroethylene/hexafluoropropylene copolymer resin, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene/ethylene Copolymer resin, polytrifluoroethylene chloride resin, polyvinylidene fluoride resin, nylon 4,6, nylon 6, nylon 6,6, nylon 6,10, nylon 6,12, nylon 12, nylon 6,T, nylon 9 , T, aromatic nylon resin, polyacetal resin, ultra-high molecular weight polyethylene resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, amorphous copolyester resin, polycarbonate resin, modified polyphenylene ether resin, thermoplastic polyurethane elastomer , polyphenylene sulfide resin, polyetheretherketone resin, liquid crystal polymer, polytetrafluoroethylene resin, polyfluoroalkoxy resin, polyetherimide resin, polysulfone resin, polyketone resin, thermoplastic polyimide resin, polyamideimide resin, polyarylate resin, polysulfone Resins, polyethersulfone resins, biodegradable resins, biomass resins include, but are not limited to. A mixture of two or more of these resins may also be used.

<(B-2) Curable resin>
The curable resin that can be used in the present invention is preferably a photo- and/or thermosetting resin. In this specification, a curable compound such as a low-molecular-weight monofunctional acrylic monomer, which does not have properties as a resin, is also described as a curable resin.
Examples of (B-2) curable resins that can be used in the present invention include (B-2-1) thermosetting resins and (B-2-2) photocurable resins.
<(B-2-1) Thermosetting resin>
Thermosetting resins include, for example, curable resins having cyclic ethers such as epoxy groups and oxetanyl groups.
The thermosetting resin having a cyclic ether is not particularly limited, and examples thereof include epoxy resins (aliphatic epoxy resins including alicyclic epoxy resins or aromatic epoxy resins), oxetane resins, furan resins, and the like. Among them, epoxy resins (which may contain an aliphatic ring, for example, an aliphatic ring having 3 to 12 carbon atoms) and oxetane resins are preferable from the viewpoint of reaction rate and versatility. The epoxy resin is not particularly limited, and examples thereof include novolak types such as phenol novolak type, cresol novolak type, biphenyl novolak type, trisphenol novolak type, and dicyclopentadiene novolak type; bisphenol A type, bisphenol F type, 2,2 '-diallyl bisphenol A type, hydrogenated bisphenol type, bisphenol type such as polyoxypropylene bisphenol A type, and the like. Other examples include glycidylamine and the like.
Examples of commercially available epoxy resins include, for example, phenolic novolac type epoxy resins such as Epiclon (registered trademark) N-740, N-770, and N-775 (all of which are manufactured by Dainippon Ink and Chemicals); Epikote (registered trademark) 152, Epikote (registered trademark) 154 (both of which are manufactured by Japan Epoxy Resin Co., Ltd.), and the like. Examples of cresol novolak type include Epiclon (registered trademark) N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP, N-672-EXP (above , both manufactured by Dainippon Ink and Chemicals Co., Ltd.); biphenyl novolac type, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); Epoxy Resin Co., Ltd.); dicyclopentadiene novolac type, for example, XD-1000-L (manufactured by Nippon Kayaku Co., Ltd.), HP-7200 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); bisphenol A type epoxy compound As, for example, Epicort (registered trademark) 828, Epicort (registered trademark) 834, Epicort 1001, Epicort (registered trademark) 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon (registered trademark) 850, Epiclon ( Registered trademark) 860, Epiclon (registered trademark) 4055 (both manufactured by Dainippon Ink and Chemicals Co., Ltd.); commercial products of bisphenol F type epoxy compounds include, for example, Epicort (registered trademark) 807 (Japan Epoxy Resin Co., Ltd. company), Epiclon (registered trademark) 830 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); 2,2'-diallyl bisphenol A type, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); hydrogenated bisphenol Examples of the type include ST-5080 (manufactured by Tohto Kasei Co., Ltd.); examples of the polyoxypropylene bisphenol A type include EP-4000 and EP-4005 (both of which are manufactured by Asahi Denka Kogyo Co., Ltd.). be done.
Commercially available products of the above oxetane compounds include, for example, Ethanacol (registered trademark) EHO, Ethanacol (registered trademark) OXBP, Ethanacol (registered trademark) OXTP, and Ethanacol (registered trademark) OXMA (all of which are manufactured by Ube Industries, Ltd.). mentioned. The alicyclic epoxy compound is not particularly limited, and examples thereof include Celoxide (registered trademark) 2021, Celoxide (registered trademark) 2080, and Celoxide (registered trademark) 3000 (all manufactured by Daicel-UCB Co., Ltd.). etc. These curable resins having a cyclic ether group may be used alone, or two or more of them may be used in combination.

<(B-2-2) Photocurable resin>
Photocurable resins include, for example, resins having a vinyl group, a vinyl ether group, an allyl group, a maleimide group, a (meth)acryloyl group, and the like. Among them, a resin having a (meth)acryloyl group, such as a (meth)acrylate compound, is preferable from the viewpoint of reactivity and versatility. In this specification, terms such as "(meth)acryloyl" mean "acryloyl" or "methacryloyl", and for example, "(meth)acrylate" means "acrylate" or "methacrylate".
Examples of resins having a (meth)acryloyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, carbitol (meth)acrylate, acryloyl Morpholine, half ester which is reaction product of hydroxyl group-containing (meth)acrylate and acid anhydride of polycarboxylic acid compound, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , trimethylolpropane polyethoxytri(meth)acrylate, glycerin polypropoxytri(meth)acrylate, di(meth)acrylate of ε-caprolactone adduct of neopentylglycol hydroxypivalate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, dipentaerythritol and ε-caprolactone reaction product poly (meth) acrylate, dipentaerythritol poly (meth) acrylate (for example, Japan Kayaku Co., Ltd., KAYARAD (registered trademark) DPHA, etc.), and (meth)acrylate compounds such as epoxy (meth)acrylate which is a reaction product of a mono- or polyglycidyl compound and (meth)acrylic acid.
The glycidyl compound used in epoxy (meth)acrylate, which is a reaction product of a mono- or polyglycidyl compound and (meth)acrylic acid, is not particularly limited. biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2′-methylene-bis(4-methyl-6-tert- butylphenol), 4,4′-butylidene-bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di-4 - Phenols having a fluorene skeleton such as hydroxyphenylfluorene, phenolized polybutadiene, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, chlorinated bisphenol Glycidyl etherified products of polyphenols such as A can be mentioned.
Epoxy(meth)acrylate, which is a reaction product of these mono- or polyglycidyl compounds and (meth)acrylic acid, can be obtained by subjecting the epoxy group to an esterification reaction with an equivalent amount of (meth)acrylic acid. This synthetic reaction can be carried out by a generally known method. For example, an equivalent amount of (meth)acrylic acid is added to resorcinol diglycidyl ether, a catalyst (e.g., benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (e.g., methoquinone, hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) to carry out an esterification reaction at, for example, 80 to 110°C. The (meth)acrylated resorcinol diglycidyl ether thus obtained is a resin having a radically polymerizable (meth)acryloyl group.

(B-2) The curable resin is preferably (B-2-1) a thermosetting resin or (B-2-2) a photocurable resin (B-2-2), which is a photocurable resin. is more preferred.
Moreover, a photocurable resin having three or more (meth)acryloyl groups in the molecule is particularly preferable.
Photocurable resins having three or more (meth)acryloyl groups and polar functional groups in the molecule include, for example, pentaerythritol triacrylate (KAYARAD PET-30 manufactured by Nippon Kayaku), dipentaerythritol pentaacrylate and dipentaerythritol. Hexaacrylate mixture (KAYARAD DPHA manufactured by Nippon Kayaku), 2-hydroxy-3-acryloyloxypropyl methacrylate (701A manufactured by Shin-Nakamura Chemical), ethoxylated isocyanuric acid triacrylate (A-9300 manufactured by Shin-Nakamura Chemical), ε- (Meth)acrylate monomer compounds such as caprolactone-modified tris-(2-acryloxyethyl) isocyanurate (A-9300-1CL Shin-Nakamura Chemical), bisphenol A type epoxy acrylates (R-115F, R-130, R-381, etc.) Nippon Kayaku), bisphenol F type epoxy acrylate (ZFA-266H Nippon Kayaku), epoxy acrylate resins such as acid-modified epoxy acrylate (ZAR series, ZCR series Nippon Kayaku), polyester urethane acrylate (UX3204, UX -4101, UXT-6100 Nippon Kayaku), mixed urethane acrylate (UX-6101, UX-8101 Nippon Kayaku), polyether urethane acrylate (UX-937, UXF-4001-M35 Nippon Kayaku) , ester-based urethane acrylate (DPHA-40H, UX-5000, UX-5102D-M20, UX-5103D, UX-5005 manufactured by Nippon Kayaku) and other urethane acrylate resins.
As a photocurable resin having 3 or more (meth)acryloyl groups in the molecule, it is more preferable to have 3 or more and 10 or less (meth)acryloyl groups, and more preferably 4 or more and 8 or less (meth)acryloyl groups. This is the case with an acryloyl group.
The content of the (B) curable resin is 0.5 to 70% by mass, preferably 5 to 40% by mass, based on the total mass of the resin composition of the present invention.

<(C) Curing agent>
The resin composition of the present invention preferably contains a curing agent as (C). In particular, when (B-2) curable resin is used as (B) transparent resin, (C) curing agent is preferably used in combination. Although the curing agent and the initiator are sometimes distinguished, both are referred to as (C) the curing agent in this specification.

When (B-2-1) thermosetting resin is used as (B-2) curable resin, it is preferable to use (C-1) thermosetting agent as component (C). However, when the (B-1) thermosetting resin is a thermosetting resin having a cyclic ether, a photocationic initiator or a photoanionic initiator that generates cations or anions upon exposure to light may also be preferably used.
(C-1) The heat curing agent is one that reacts nucleophilically with an unshared electron pair or an anion in the molecule, such as an amine curing agent (hereinafter also referred to as amines), a hydrazide curing agent. (hereinafter also referred to as hydrazides), imidazole-based curing agents (hereinafter also referred to as imidazoles), polyamide resins, dicyandiamide, isocyanates, thiol-based curing agents (thiols), phenol-based curing agents (phenols), and the like. . However, it is not limited to these.
Examples of amines include aliphatic chain amines, aliphatic cyclic amines, aromatic amines, and modified amines (amine adducts, ketimine, etc.). Any of primary amines, secondary amines, tertiary amines and quaternary amines may be used, but primary or secondary amines are preferred from the viewpoint of reactivity.
Specific examples of amines include diaminodiphenylmethane, diaminodiphenylsulfone, 4,4′-diamino-3,3′-dimethyldiphenylmethane, diaminodiphenyl ether, diethylmethylbenzenediamine, 2-methyl-4,6-bis(methylthio )-1,3-benzenediamine, bisaniline, diethyltoluenediamine, aromatic amines such as diethylthiotoluenediamine, N,N'-bis(sec-butylamino)diphenylmethane, methylamine, dimethylamine, trimethylamine, ethylamine, Aliphatic amines such as diethylamine, triethylamine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, norbornanediamine, polyetheramine, triethylenetetramine, and tetraethylenepentamine, and modified amines. Diethylmethylbenzenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, and diethyltoluenediamine are particularly preferred.
As hydrazides, organic acid hydrazide compounds are particularly preferably used. For example, the aromatic hydrazides salicylic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridine dihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8 - naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like. Examples of aliphatic hydrazide compounds include formhydrazide, acetohydrazide, propionic hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N,N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis( a dihydrazide compound having a hydantoin skeleton such as hydrazinocarbonoethyl)-5-isopropylhydantoin, preferably a valine hydantoin skeleton (a skeleton in which a carbon atom of the hydantoin ring is substituted with an isopropyl group), tris(1-hydrazinocarbonylmethyl) isocyanurate, tris(2-hydrazinocarbonylethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris(3-hydrazinocarbonylpropyl)isocyanurate, bis(2-hydrazinocarbonylethyl)isocyanurate etc. can be given. From the balance between curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, tris(hydrazinocarbonylmethyl)isocyanurate, tris(1-hydrazinocarbonylethyl)isocyanurate, tris(2- hydrazinocarbonylethyl)isocyanurate, tris(3-hydrazinocarbonylpropyl)isocyanurate, particularly preferably tris(2-hydrazinocarbonylethyl)isocyanurate.
Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1') ) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-ethyl, 4-methylimidazole ( 1′)) Ethyl-s-triazine, 2,4-diamino-6(2′-methylimidazole (1′))ethyl-s-triazine isocyanuric acid adduct, 2:3 addition of 2-methylimidazole isocyanuric acid 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyano Examples include various imidazoles of ethoxymethylimidazole, and salts of these imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and oxalic acid. be done.
Examples of thiols include Karenz MT PE1, BD1, NR1, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) (all manufactured by Showa Denko K.K.), and the like. can be done. A thiol-based curing agent is a curing agent having at least one thiol group (SH) in its molecule.
Examples of phenols include phenol novolaks, bisphenol A, bisphenol S, and the like obtained by condensation reaction of phenol (which may have various substituents) with formalin in the presence of an acid catalyst.
When (C-1) thermosetting agent is used in the resin composition of the present invention, the functional group equivalent to the thermosetting resin is preferably 0.4 functional group equivalent or more and 4.0 functional group equivalent or less, more preferably It is 0.6 or more functional group equivalents and 3.0 functional group equivalents, and particularly preferably 0.8 or more functional group equivalents and 2.0 or less functional group equivalents.

When a thermosetting agent is used, a thermosetting accelerator may be used together. Examples of curing accelerators include phenols, organic acids, phosphines, imidazole, and the like.
Examples of the organic acid include organic carboxylic acid and organic phosphoric acid, and organic carboxylic acid is preferable. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid , cyclohexanedicarboxylic acid, tris(2-carboxymethyl)isocyanurate, tris(2-carboxyethyl)isocyanurate, tris(2-carboxypropyl)isocyanurate, bis(2-carboxyethyl)isocyanurate and the like. .
Examples of phosphines include triphenylphosphine and tetraphenylphosphonium tetraphenylborate.
Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1')) Ethyl-s-triazine, 2,4-diamino-6(2'-undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6(2'-ethyl-4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6(2'-methylimidazole (1'))ethyl-s-triazine isocyanuric acid adduct, 2:3 adduct of 2-methylimidazole isocyanuric acid , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxy and methylimidazole.
When a thermosetting accelerator is used in the resin composition of the present invention, it is preferably from 0.0001% by mass to 5.0% by mass, more preferably from 0.001% by mass to 5.0% by mass, based on the total amount of the transparent resin. It is 0 mass % or less, and particularly preferably 0.1 mass % or more and 1.0 mass % or less.

<(C-2) Photoinitiator>
When (B-2-2) photocurable resin is used as (B-2) curable resin, (C-2) photoinitiator is preferably used in combination as component (C). However, since the (B-2-2) photocurable resin has a functional group that undergoes a chain polymerization reaction with a radical such as a double bond, the use of a thermal radical initiator that generates radicals by heat, for example, is excluded. not something.
(C-2) The photoinitiator is preferably a photoradical polymerization initiator. This is not particularly limited as long as it is a compound that generates radicals and initiates a chain polymerization reaction upon irradiation with ultraviolet rays or visible light. anthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone , 9-fluorenone, diphenyl disulfide and the like. Specifically, IRGACURE ^RTM 651, 184, 2959, 127, 907, 369, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE ^RTM 1173, LUCIRIN ^RTM TPO (all manufactured by BASF), Seikuol ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Kagaku Co., Ltd.) and the like.
Further, the molar extinction coefficient (ε) at 365 nm is preferably 50 or more and 10000 (mL/g cm) or less, more preferably 100 or more and 8000 (mL/g cm) or less, and 1000 or more and 7500 ( mL/g·cm) or less is particularly preferred. The molar extinction coefficient is measured using methanol or acetonitrile as a solvent.
Photopolymerization initiators having a molar extinction coefficient (ε) at 365 nm of 100 or more and 10000 (mL/g cm) or less include IRGACURE ^RTM 651 (ε in methanol = 360 mL/g cm), IRGACURE ^RTM 907 (in methanol ε = 4700 mL/g cm), IRGACURE ^RTM 369 (ε = 7900 mL/g cm in methanol), IRGACURE ^RTM 379 (ε = 7900 mL/g cm in methanol), IRGACURE ^RTM 819 (ε = 2300 mL/g in methanol cm), IRGACURE ^RTM TPO (ε in acetonitrile = 4700 mL/g cm), IRGACURE ^RTM OXE-01 (ε in acetonitrile = 7000 mL/g cm), IRGACURE ^RTM OXE-02 (ε in acetonitrile = 7700 mL/g cm). cm), etc., but is not limited to these.
When a radical photopolymerization initiator is used, its content is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the binder resin.
The preferred upper limit of this content is 7 parts by mass, more preferably 5 parts by mass, particularly preferably 4 parts by mass, and most preferably 3 parts by mass.
A preferred lower limit is 0.01 parts by mass, more preferably 0.1 parts by mass, particularly preferably 1 part by mass, and most preferably 1.5 parts by mass.

<Thermal radical polymerization initiator>
(B-2-2) When a thermal radical polymerization initiator is used for the photocurable resin, the thermal radical polymerization initiator is particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction. Although not used, organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacol and the like can be mentioned, and benzopinacol is preferably used. For example, organic peroxides include Kayamec (registered trademark) A, M, R, L, LH, SP-30C, Perkadox CH-50L, BC-FF, Kadox B-40ES, Perkadox 14, and Trigonox ^RTM 22. -70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester ^RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl ^RTM B, Perkadox 16, Kayacarvone (registered trademark) BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec (registered trademark) N, H, S, F, D, G, Perhexa (registered trademark) H, HC , TMH, C, V, 22, MC, Percure (registered trademark) AH, AL, HB, Perbutyl (registered trademark) H, C, ND, L, Percumyl (registered trademark) H, D, Perloyl (registered trademark) IB , IPP, and Perocta (registered trademark) ND (manufactured by NOF Corporation) are commercially available. As azo compounds, VA-044, V-070, VPE-0201, VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are commercially available.
When a thermal radical polymerization initiator is used, its content is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the binder resin.
The preferred upper limit of this content is 7 parts by mass, more preferably 5 parts by mass, particularly preferably 4 parts by mass, and most preferably 3 parts by mass.
A preferred lower limit is 0.01 parts by mass, more preferably 0.1 parts by mass, particularly preferably 1 part by mass, and most preferably 1.5 parts by mass.
The most preferable range for the content in the resin composition is 1.5 parts by mass or more and 3 parts by mass or less.

The content of (A) metal oxide hollow particles is preferably 0.1 to 90% by mass with respect to the total mass of the resin composition of the present invention. The upper limit of the content is more preferably 80% by mass, more preferably 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, and particularly preferably 50% by mass. The lower limit is more preferably 1% by mass, more preferably 5% by mass, 8% by mass, 10% by mass, 12% by mass, and particularly preferably 15% by mass. Therefore, the most preferable content of (A) metal oxide hollow particles is 15% by mass or more and 50% by mass or less. If the content is too low, blue light cannot be blocked, and if the content is too high, the visible light transmittance decreases, which is not preferable.

<Other ingredients>
The resin composition of the present invention contains, in addition to the above components (A) to (C), a solvent, a dispersant, a surfactant, powder, a water-soluble polymer, an ultraviolet absorber, a sequestering agent, an amino acid, and a polymer emulsion. , a pH adjuster, an antioxidant, an antioxidant assistant, etc., can be appropriately contained as necessary.

<Solvent>
The resin composition of the present invention may contain a solvent.
Solvents that can be used may be water-soluble or water-insoluble.
Examples of water-insoluble solvents include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetylacetone, etc.), and ester solvents. (ethyl acetate, methyl acetate, butyl acetate, cellosolve acetate, amyl acetate, etc.), ether solvents (isopropyl ether, methyl cellosolve, butyl cellosolve, 1,4-dioxane, etc.), glycol ether solvents (diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), glycol ester solvents (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), glyme solvents (monoglyme, diglyme, etc.), halogen solvents (dichloromethane, chloroform, etc.), tetrahydrofuran are mentioned.
Examples of water-soluble solvents include C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol and tert-butanol; N,N-dimethylformamide, N,N-dimethylacetamide and the like. Carboxylic acid amide; Lactam such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidin-2-one, 1,3-dimethylhexahydropyrimido- Cyclic ureas such as 2-one; ketones or ketoalcohols such as acetone, 2-methyl-2-hydroxypentan-4-one, ethylene carbonate; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, diethylene glycol, 1,2 -propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-hexanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol, C2-C6 diols such as propylene glycol, polyethylene glycol with a molecular weight of 400, 800, 1540 or higher, polypropylene glycol, thiodiglycol, dithiodiglycol, or mono-, oligo- or polyalkylene glycols having C2-C6 alkylene units or thioglycol; polyols (triols) such as glycerin, diglycerin, hexane-1,2,6-triol and trimethylolpropane; dimethyl sulfoxide; propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propio ethylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol monoethyl ether butyrate, ethylene glycol monobutyl ether butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol Glycol ethers such as monomethyl ether butyrate and dipropylene glycol monomethyl ether butyrate, or glycol ether acetates;

The above water-soluble organic solvents also include substances that are solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it exhibits water solubility, and an aqueous solution containing the substance or the like exhibits properties similar to those of a water-soluble organic solvent, and can be used with the expectation of the same effect. For this reason, in the present specification, for the sake of convenience, even such solid substances are included in the category of water-soluble organic solvents as long as they can be used with the expectation of the same effect as described above.

Preferred water-soluble organic solvents include isopropanol, glycerin, mono-, di-, triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane, and butyl carbitol, more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and butyl carbitol. These water-soluble organic solvents are used singly or in combination.
It is preferable that the content of the solvent is 1 to 90% by mass with respect to the total mass of the resin composition of the present invention. In the above (A) resin composition using metal oxide hollow particles, (B) the transparent resin, (C) the curing agent and other components are used in appropriate amounts. The remainder can be a solvent.
The upper limit of the content is more preferably 80% by mass, still more preferably 60% by mass, and particularly preferably 40% by mass. Moreover, as a lower limit, 10 mass % is more preferable, 20 mass % is still more preferable, and 30 mass % is especially preferable. Therefore, the most preferable content of the solvent is 30% by mass or more and 40% by mass or less.

<Dispersant>
Dispersants include fatty acid salts (soap), α-sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), and alkyl ether sulfates. salt (AES), low-molecular-weight anionic (anionic) compounds such as triethanol alkyl sulfates, fatty acid ethanolamides, polyoxyethylene alkyl ethers (AE), polyoxyethylene alkylphenyl ethers (APE), low-molecular-weight compounds such as sorbitol and sorbitan Nonionic compounds, low-molecular-weight cationic (cationic) compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium chlorides, and alkylpyridinium chlorides, low-molecular-weight amphoteric compounds such as alkylcarboxylbetaine, sulfobetaine, and lecithin, and naphthalenesulfonic acid Formalin condensates of salts, polystyrene sulfonates, polyacrylates, copolymer salts of vinyl compounds and carboxylic acid monomers, carboxymethyl cellulose, polymeric aqueous dispersants represented by polyvinyl alcohol, polyacrylic acid Polymeric non-aqueous dispersants such as partial alkyl esters and polyalkylenepolyamines, and polymeric cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers are typical examples, and are preferably applied to the resin composition of the present invention. As long as it is possible, it does not exclude those having a structure other than the one illustrated here.

Specific names of dispersants to be added are as follows. Floren DOPA-15B, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse AX5, Solsperse TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000,ソルスパース３２０００、ソルスパース３５１００、ソルスパース５４０００、ソルシックス２５０、（日本ルーブリゾール株式会社製）、ＥＦＫＡ４００８、ＥＦＫＡ４００９、ＥＦＫＡ４０１０、ＥＦＫＡ４０１５、ＥＦＫＡ４０４６、ＥＦＫＡ４０４７、ＥＦＫＡ４０６０、ＥＦＫＡ４０８０、ＥＦＫＡ７４６２、ＥＦＫＡ４０２０、ＥＦＫＡ４０５０、ＥＦＫＡ４０５５、ＥＦＫＡ４４００、ＥＦＫＡ４４０１、ＥＦＫＡ４４０２、ＥＦＫＡ４４０３、ＥＦＫＡ４３００、ＥＦＫＡ４３２０、ＥＦＫＡ４３３０、ＥＦＫＡ４３４０、ＥＦＫＡ６２２０、ＥＦＫＡ６２２５、ＥＦＫＡ６７００、ＥＦＫＡ６７８０、ＥＦＫＡ６７８２、ＥＦＫＡ８５０３（エフカアディディブズ社製）、アジスパーＰＡ１１１、アジスパーＰＢ７１１、アジスパーＰＢ８２１、アジスパーＰＢ８２２、アジスパーＰＮ４１１、フェイメックスＬ－１２（味の素ファインテクノ株式会社製）、ＴＥＸＡＰＨＯＲ－ＵＶ２１、ＴＥＸＡＰＨＯＲ－ＵＶ６１（コグニスジャパン株式会社製）、ＤｉｓｐｅｒＢＹＫ１０１、ＤｉｓｐｅｒＢＹＫ１０２、ＤｉｓｐｅｒＢＹＫ１０６、ＤｉｓｐｅｒＢＹＫ１０８、ＤｉｓｐｅｒＢＹＫ１１１、ＤｉｓｐｅｒＢＹＫ１１６、ＤｉｓｐｅｒＢＹＫ１３０、ＤｉｓｐｅｒＢＹＫ１４０、ＤｉｓｐｅｒＢＹＫ１４２、ＤｉｓｐｅｒＢＹＫ１４５、ＤｉｓｐｅｒＢＹＫ１６１、ＤｉｓｐｅｒＢＹＫ１６２、ＤｉｓｐｅｒＢＹＫ１６３、ＤｉｓｐｅｒＢＹＫ１６４、ＤｉｓｐｅｒＢＹＫ１６６、ＤｉｓｐｅｒＢＹＫ１６７、ＤｉｓｐｅｒＢＹＫ１６８、ＤｉｓｐｅｒＢＹＫ１７０、ＤｉｓｐｅｒＢＹＫ１７１、ＤｉｓｐｅｒＢＹＫ１７４、ＤｉｓｐｅｒＢＹＫ１８０、ＤｉｓｐｅｒＢＹＫ１８２、ＤｉｓｐｅｒＢＹＫ１９２、ＤｉｓｐｅｒＢＹＫ１９３、ＤｉｓｐｅｒＢＹＫ２０００、ＤｉｓｐｅｒＢＹＫ２００１、ＤｉｓｐｅｒＢＹＫ２０２０、ＤｉｓｐｅｒＢＹＫ２０２５、ＤｉｓｐｅｒＢＹＫ２０５０、ＤｉｓｐｅｒＢＹＫ２０７０、ＤｉｓｐｅｒＢＹＫ２１５５、ＤｉｓｐｅｒＢＹＫ２１６４、ＢＹＫ２２０Ｓ、ＢＹＫ３００、ＢＹＫ３０６、ＢＹＫ３２０、ＢＹＫ３２２、ＢＹＫ３２５、ＢＹＫ３３０、ＢＹＫ３４０、ＢＹＫ３５０、ＢＹＫ３７７、ＢＹＫ３７８、ＢＹＫ３８０Ｎ、ＢＹＫ４１０、ＢＹＫ４２５、ＢＹＫ４３０（ビックケミー・ジャパン株式会社製）、ディスパロン１７５１Ｎ、ディスパロン１８３１、ディスパロン１８５０ , Disparlon 1860, Disparlon 1934, Disparlon DA-400N, Disparlon DA-703-50, Disparlon DA-725, Disparlon DA-705, Disparlon DA-7301, Disparlon DN-900, Disparlon NS-5210, Disparlon NVI-8514L, Hip Lard ED-152, HIPRAD ED-216, HIPRAD ED-251, HIPRAD ED-360 (Kusumoto Kasei Co., Ltd.), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX -710LL, FTX-750LL, Futergent 212P, Futergent 220P, Futergent 222F, Futergent 228P, Futergent 245F, Futergent 245P, Futergent 250, Futergent 251, Futergent 710FM, Futergent 730FM, Futergent 730LL , Futergent 730LS, Futergent 750DM, Futergent 750FM (manufactured by Neos Co., Ltd.), AS-1100, AS-1800, AS-2000 (manufactured by Toagosei Co., Ltd.), Kaosera 2000, Kaosera 2100, KDH-154, MX- 2045L, Homogenol L-18, Homogenol L-95, Rhodol SP-010V, Rhodol SP-030V, Rhodol SP-L10, Rhodol SP-P10 (manufactured by Kao Corporation), Evan U103, Cyanol DC902B, Neugen EA-167, Bligh Surf A219B, Brysurf AL (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Megaface F-477, Megaface 480SF, Megaface F-482, (manufactured by DIC Corporation), Silface SAG503A, Dynor 604 (Nissin Chemical Industry Co., Ltd.), SN Spurs 2180, SN Spurs 2190, SN Leveler S-906 (manufactured by San Nopco Co., Ltd.), S-386, S-420 (AGC Seimi Chemical Co., Ltd. manufactured by a company) can be exemplified.

<Surfactant>
Examples of surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, lipophilic nonionic surfactants, and hydrophilic nonionic surfactants. The content of the surfactant is 0 to 20% by mass, preferably 5 to 15% by mass, based on the total mass of the resin composition of the present invention.
(Anionic surfactant)
Examples of anionic surfactants include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (e.g., , POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (e.g., sodium lauroyl sarcosinate, etc.); -myristoyl-N-methyltaurate sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); phosphate ester salts (POE-oleyl ether phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinates (For example, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); sulfonic acid triethanolamine, linadodecylbenzene sulfonic acid, etc.); higher fatty acid ester sulfate salts (eg, hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); disodium stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (e.g. funnel oil, etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate higher fatty acid ester sulfonate; secondary alcohol sulfate; higher fatty acid alkylolamide sulfate; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartic acid ditriethanolamine; .
(Cationic surfactant)
Cationic surfactants include, for example, alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts; Poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salts; alkyldimethylbenzylammonium salts; alkylisoquinolinium salts; dialkylmorphonium salts; POE-alkylamines; alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.
(Amphoteric surfactant)
sil-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); betaine-based surfactants (e.g. , 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amidobetaine, sulfobetaine, etc.).
(Lipophilic nonionic surfactant)
Lipophilic nonionic surfactants include, for example, sorbitan fatty acid esters (e.g., sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate, etc.); , α,α'-pyroglutamic acid glyceryl monostearate, glycerol monostearate, malic acid, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.); hydrogenated castor oil derivatives;
(Hydrophilic nonionic surfactant)
Hydrophilic nonionic surfactants include, for example, POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE-sorbitol fatty acid esters (eg, POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerol mono stearate, POE-monooleate such as POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.); POE-fatty acid esters (e.g., POE-distearate, POE-monodioleate, ethylene glycol distearate, etc.); Alkyl ethers (eg, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic (registered trademark), etc.); POE POP-alkyl ether (e.g., POE POP-cetyl ether, POE POP-2-decyltetradecyl ether, POE POP-monobutyl ether, POE POP-hydrogenated lanolin, POE/POP-glycerin ether, etc.); TetraPOE/tetraPOP-ethylenediamine condensate (e.g., Tetronic, etc.); POE-castor oil hydrogenated castor oil derivatives (e.g., POE-castor oil, POE-hydrogenated castor oil, POE- hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic monoisostearate diester, POE-hydrogenated castor oil maleic acid, etc.); POE-beeswax lanolin derivatives (for example, POE-Sorbit beeswax, etc.); alkanolamides (e.g., coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; ester; alkylethoxydimethylamine oxide; trioleyl phosphate and the like.
The surfactant content is 0 to 20% by weight, preferably 5 to 15% by weight, relative to the total weight of the dispersion of the invention.

<Powder>
As the powder, apart from the component (A) metal oxide hollow particles, if it is used in ordinary resin compositions, its shape (spherical, needle-like, plate-like, etc.) and particle size (fumes, fine particles, etc.) , pigment grade, etc.) and particle structure (porous, non-porous, etc.). Inorganic powders such as magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, synthetic mica, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite , Lethia mica, Silicic acid, Silicic anhydride, Aluminum silicate, Magnesium silicate, Magnesium aluminum silicate, Calcium silicate, Barium silicate, Strontium silicate, Metal tungstate, Hydroxyapatite, Vermiculite, Hysilite, Montmorillonite , zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, silica, zinc oxide, zirconium oxide, titanium oxide, boron nitride, boron nitride, etc.; organic powders such as polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, nylon powder, nylon 12 powder, nylon 6 powder, styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymer powder, vinyl resin powder, urea resin powder, phenolic resin powder, fluorine resin powder, silicone resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, lauroyl lysine, etc.; as colored pigments, for example, inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic black pigments such as iron oxide and carbon black; inorganic purple pigments such as manganese violet and cobalt violet; inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; , lakes of tar-based pigments, lakes of natural pigments, composite powders obtained by combining these powders, etc.; pearl pigments such as titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride , titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scale foil, titanium oxide-coated colored mica, etc.; metal powder pigments such as aluminum powder, copper powder -, stainless steel powder, etc.; tar pigments such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227 , Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207; natural pigments such as carmine acid, laccaic acid, calsamine, brazilin, crocin and the like. It should be noted that these powders may be combined, or powders surface-treated with an oil agent, silicone, fluorine compound, or the like may be used.

<Water-soluble polymer>
Both natural and synthetic water-soluble polymers can be used, and they can be used in combination.
Examples of natural water-soluble polymers include plant-based polymers (e.g., gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algecolloid (cassou extract), starch (rice, corn, potato, wheat), glycyrrhizic acid); microbial macromolecules (e.g., xanthan gum, dextran, succinoglucan, bullulan, etc.); animal macromolecules (e.g., collagen, casein, albumin, gelatin, etc.), etc. is mentioned.
Examples of synthetic water-soluble polymers include starch-based polymers (e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); polyvinyl pyrrolidone, carboxyvinyl polymer, etc.); , sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymer;

<Ultraviolet absorber>
Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (e.g., para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, , N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); Salicylic acid-based UV absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid-based UV absorbers (e.g., octyl methoxycinnamate, ethyl -4-isopropylcinnamate, methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl -α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone-based ultraviolet absorbers (e.g., 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl- benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3-(4′-methylbenzylidene)-d,l-camphor, 3 -benzylidene-d,l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole;2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole;2-(2'-hydroxy-5-methylphenylbenzotriazole;dibenzalazine;dianisoylmethane;4-methoxy-4'-t-butyldibenzoylmethane; 5-(3,3-dimethyl-2-norbornylidene )-3-pentan-2-one, dimorpholinopyridazino; 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; 2,4-bis-{[4-(2-ethylhexyloxy)-2- hydroxy]-phenyl}-6-(4-methoxyphenyl)-(1,3,5)-triazine and the like.

<Sequestering agent>
Examples of sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. , sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate, and the like.

<Amino acid>
Amino acids include, for example, neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include sodium acyl sarcosinate (sodium lauroyl sarcosinate), acyl glutamate, sodium acyl β-alanine, glutathione, pyrrolidone carboxylic acid and the like.

<Organic amine>
Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. is mentioned.

<Polymer emulsion>
Examples of polymer emulsions include acrylic resin emulsions, polyethyl acrylate emulsions, acrylic resin liquids, polyacryl alkyl ester emulsions, polyvinyl acetate resin emulsions, and natural rubber latex.

<pH adjuster>
Examples of pH adjusters include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

<Antioxidant>
Examples of antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.

<Antioxidant aid>
Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

[Use]
The resin composition of the present invention is characterized in that it efficiently cuts blue light having a wavelength of around 450 nm and has excellent transmittance of other wavelengths. Therefore, it is very useful for eyewear applications, for example. Especially for eyewear applications, it is effective for cutting blue light emitted from electronic devices such as personal computers, smartphones, tablets, and communication devices to reduce the burden on the eyes, and for protective glasses after cataract surgery. be done.

It is also useful for optical element applications such as members for light-emitting devices, light-scattering films, quantum dot color resists, light-shielding resists, and adhesives for electronic parts.
For example, as a member for a light-emitting device, a cured film obtained by curing the resin composition of the present invention can selectively scatter blue light in particular by adjusting the particle diameter and hollow diameter of the hollow-structured particles. It becomes a component for equipment. In particular, it is suitably used for display devices such as liquid crystal displays and organic EL displays.
The light-scattering film is useful because the metal oxide hollow particles in the resin composition of the present invention are uniform in shape and particle size, so that a layer that generates uniform scattered light can be formed.
In the quantum dot color resist, the hollow particles in the resin composition of the present invention can efficiently guide the light to the quantum dots by multiple scattering of the light emitted from the light source, and can increase the emission intensity. It is useful because it has better sedimentation stability than titanium oxide particles.
The light-shielding resist efficiently shields light by multiple scattering caused by the hollow particles in the resin composition of the present invention, and is therefore useful as a light-shielding partitioning agent for micro LEDs and the like.

[Cured film]
Among the above uses, a cured film obtained by curing the resin composition of the present invention is very useful for use as a film (membrane). Examples of methods for producing this cured film include comma coaters, spray coaters, roll coaters, knife coaters, bar coaters, spin coaters, die coaters, micro gravure coaters, screen printing, dispensers, curtain coaters, dip coaters, inkjets, laminates, and the like. After coating by a transfer method or the like, it is photocured by irradiating ultraviolet rays of about 100 to 10,000 mJ/cm ² , more preferably 1,000 to 6,000 mJ/cm ² with an ultraviolet irradiator, or 50 to 200° C., more preferably 80° C. It can be produced by heat curing at about 130° C. for 0.1 hour to 5 hours, more preferably about 0.5 to 2 hours, or by combining the above photocuring and heat curing.
In the evaluation, a cured film with a thickness of 5 μm is produced, but when used as a blue light cut film, it is preferably about 1 μm to 300 μm. It is more preferably about 2 μm to 200 μm, still more preferably about 3 μm to 100 μm, and particularly preferably about 4 μm to 50 μm.

[Method for producing resin composition]
As an example of the method for obtaining the resin composition of the present invention, there is the method shown below. First, the component (B) and other components used as necessary are mixed and dissolved. If necessary, it may be melted by heating. Next, component (A) and, if necessary, component (C) are added, uniformly mixed with a known mixing device such as a three-roll mill, sand mill, ball mill, bead mill, etc., and filtered through a metal mesh to obtain the present invention. of the resin composition can be produced.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. It should be noted that the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
In the examples or comparative examples, when the desired amount of the substance could not be obtained by a single synthesis operation, etc., the synthesis operation, etc. was repeated until the desired amount of the substance was obtained.
The primary particle diameter of the hollow structure particles, the inner diameter of the hollow structure, and the state of collapse after the preparation of the hollow structure particles were measured using a transmission electron microscope (JEM-2800, manufactured by JEOL Ltd.).
In addition, the content of rutile-type titanium oxide was calculated according to the following formula (5) using a powder X-ray diffractometer (X'Pert PRO manufactured by Spectris Co., Ltd.).
Spectroscopic measurement of the produced blue light cut film was performed by measuring the transmittance at wavelengths of 380 nm to 780 nm using a spectrophotometer (Shimadzu Corporation UV-3100).

Abbreviations and the like in the following formula (5) have the following meanings.
F _R : content of rutile-type titanium oxide (% by mass)
I _A (101): Intensity of the (101) face of the anatase crystal measured with a powder X-ray diffractometer I _R (110): Intensity of the (110) face of the rutile crystal measured with a powder X-ray diffractometer

[Synthesis Example 1: Preparation of Ethanol Dispersion of Template Particles (Dispersion 1)]
15 g of styrene, 2.4 g of methacrylic acid, and 0.05 g of potassium persulfate were added to 600 g of distilled water, and emulsion polymerization was carried out at 80° C. to obtain an aqueous dispersion containing styrene-methacrylic acid polymer particles (template particles). . The primary particle diameter of the obtained template particles was 180 nm. Dispersion 1 was prepared by adding ethanol while concentrating an aqueous dispersion of template particles with an evaporator to replace water with ethanol. The content of template particles in Dispersion 1 was 9% by mass.

[Synthesis Example 2: Preparation of Ethanol Dispersion of Template Particles (Dispersion 2)]
Dispersion 2 was prepared in the same manner as in Synthesis Example 1 except that 15 g of styrene used in Synthesis Example 1 was changed to 20 g. The primary particle diameter of the obtained template particles was 230 nm. The content of template particles in Dispersion Liquid 2 was 10% by mass.

[Synthesis Example 3: Preparation of Ethanol Dispersion of Template Particles (Dispersion 3)]
Dispersion 3 was prepared in the same manner as in Synthesis Example 1, except that 15 g of styrene used in Synthesis Example 1 was changed to 10 g, and the synthesis temperature was changed from 80°C to 92°C. The primary particle diameter of the obtained template particles was 120 nm. Further, the content of the template particles in Dispersion 3 was 7% by mass.

[Synthesis Example 4: Preparation of Ethanol Dispersion of Template Particles (Dispersion 4)]
Dispersion 4 was prepared in the same manner as in Synthesis Example 1 except that 0.05 g of potassium persulfate used in Synthesis Example 1 was changed to 0.1 g. The primary particle diameter of the obtained template particles was 150 nm. Further, the content of the template particles in the dispersion liquid 4 was 9% by mass.

[Example 1]
(Step 1: Step of Obtaining First Core/Shell Particles)
20 g of ethanol, 8 g of acetonitrile, and Dispersion 1 (5 g) were cooled to 10° C. to obtain a liquid. To this liquid, 1.5 g of titanium tetrabutoxide and 1 g of 2% aqueous ammonia were added in three portions at intervals of 0.5 hours, and reacted at 10° C. for 4 hours to form the first core/shell particles. I got the liquid. The resulting liquid was used in the next step 2 without isolation and purification.

(Step 2: Step of obtaining second core/shell particles)
To the liquid obtained in step 1, 0.03 g of tetraethyl orthosilicate and 7 g of distilled water were added at 25°C and reacted at 25°C for 10 hours to obtain a liquid. The resulting liquid was centrifuged at 15,000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60°C to obtain 1.0 g of the desired second core/shell particles. Obtained.

(Step 3: Step of producing hollow structure particles)
Example 1 containing titanium oxide and silica by placing 1.0 g of the second core/shell particles obtained in step 2 on a ceramic board, setting it in a firing furnace, and firing in an air atmosphere of 1000° C. for 1 hour. 0.5 g of hollow-structured particles of FIG. 1 shows an SEM image and EDS data of the hollow structure particles.

(Step 4: Step of producing a resin composition for cutting blue light)
1.92 g of hollow structure particles prepared in step 3, 7 g of dipentaerythritol poly(meth)acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, Irgacure) as a photoinitiator 184) 0.5 g, 0.2 g of DISPERBYK-168 (manufactured by BYK-Chemie Japan Co., Ltd.) as a dispersant, and 10 g of propylene glycol monomethyl ether acetate as a solvent were mixed, and a disperser (Filmix, manufactured by Primix Co., Ltd.) was used. A blue light cutting resin composition 1 of the present invention was prepared.

(Step 5: Step of manufacturing a blue light cut film)
After leaving the blue light cut composition 1 prepared in step 4 for 1 day, a spin coater was used on a 100 μm PET substrate (Cosmoshine A4360, manufactured by Toyobo Co., Ltd.) so that the film thickness after heat treatment was 5 μm. and dried at 100° C. for 2 minutes using a hot plate. Then, the blue light cut film 1 of the present invention having a film thickness of 5 μm was produced by UV irradiation.

[Example 2]
Blue was prepared in the same manner as in Example 1 except that Dispersion 1 used in Example 1 was changed to Dispersion 2, 1.5 g of titanium tetrabutoxide was changed to 1.0 g, and 0.03 g of tetraethyl orthosilicate was changed to 0.02 g. A light-cutting resin composition 2 and a blue light-cutting film 2 were prepared.

[Example 3]
Blue was prepared in the same manner as in Example 1 except that Dispersion 1 used in Example 1 was changed to Dispersion 3, 1.5 g of titanium tetrabutoxide was changed to 4.0 g, and 0.03 g of tetraethyl orthosilicate was changed to 0.08 g. A light-cutting resin composition 3 and a blue light-cutting film 3 were prepared.

[Example 4]
A blue light cutting resin composition 4 and a blue light cutting film were prepared in the same manner as in Example 1 except that the dispersion liquid 1 used in Example 1 was changed to the dispersion liquid 2 and 0.03 g of tetraethyl orthosilicate was changed to 0.14 g. 4 was produced.

[Example 5]
Blue light cutting resin composition 5 and blue light cutting resin composition 5 and blue A light cut film 5 was produced.

[Example 6]
The procedure of Example 1 was repeated except that 1.78 g of the hollow structure particles used in Example 1 were changed to 5.36 g, and 0.2 g of DISPERBYK-168 (manufactured by BYK-Chemie Japan Co., Ltd.) as a dispersant was changed to 0.5 g. Blue light cut resin composition 6 and blue light cut film 6 were produced.

[Example 7]
Resin composition 7 for cutting blue light and blue A light cut film 7 was produced.

[Example 8]
Dispersion 1 used in Example 1 to Dispersion 4, 1.5 g of titanium tetrabutoxide to 1.2 g, 0.03 g of tetraethyl orthosilicate to 1.25 g, and fired in an air atmosphere at 1000° C. for 1 hour in a hydrogen atmosphere. Below, after baking at 800 ° C. for 1 hour, the hydrogen atmosphere was replaced with an air atmosphere, and the blue light cutting resin composition 8 and blue light cutting were performed in the same manner as in Example 1 except that the baking was changed to 1000 ° C. for another 1 hour. Film 8 was produced.

[Comparative Example 1]
Dispersion 1 used in Example 1 was changed to 5 g of ethanol, 1.5 g of titanium tetrabutoxide to 3.0 g, 0.03 g of tetraethyl orthosilicate to 0.06 g, and 1 g of 2% aqueous ammonia to 1% aqueous ammonia. A comparative blue light blocking resin composition 1 and a comparative blue light blocking film 1 were produced in the same manner as in Example 1 except that

[Comparative Example 2]
Comparative blue light blocking resin composition 2 and A comparative blue light cut film 2 was produced.

The results of Examples and Comparative Examples are summarized in Table 1 below.

From Table 1, it can be seen that the examples sufficiently block transmitted light with a wavelength of 400 nm (light that shows minimal transmittance at a wavelength of 400 nm to 500 nm in the evaluation sample), while transmitting light with a wavelength of 600 nm. It can be suitably used as a filter or eyewear. In addition, it can be confirmed that in Example 8, the silica content is large and the blue light cut performance is slightly inferior.
On the other hand, in Comparative Examples 1 and 2, since both the transmitted light of 400 nm and the transmitted light of 600 nm are blocked, it can be confirmed that the visibility becomes unclear.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2021-31653) filed on March 1, 2021, the entirety of which is incorporated by reference. Also, all references cited herein are incorporated in their entirety.

The resin composition of the present invention has superior light-blocking properties at specific wavelengths compared to conventional compositions containing metal oxides or titanium oxide fine particles, while also having excellent light-transmitting properties at other wavelengths. Therefore, it is suitably used for wavelength-selectively shielding applications, particularly blue light cutting applications for eyewear.

Claims

(A) metal oxide hollow particles, and (B) a resin composition for cutting blue light containing a transparent resin,
A resin composition for cutting blue light, wherein A and B satisfy the following formulas (1) and (2), where A (nm) is the hollow diameter and B (nm) is the particle diameter of (A).

0.65≦A/B≦0.9 (1)
100 nm ≤ B ≤ 250 nm (2)
When X (%) is the minimum transmittance at a wavelength of 400 nm to 500 nm and Y (%) is the transmittance at 600 nm when measured as a film with a thickness of 5 μm, X and Y are represented by the following formulas (3) and ( 4) The resin composition for cutting blue light according to claim 1, which satisfies 4).

0%≦X≦60% (3)
0.25≦X/Y≦0.8 (4)
The resin composition for cutting blue light according to claim 1 or 2, wherein the (A) metal oxide hollow particles are (A-1) hollow particles containing rutile-type titanium oxide.
The blue light cut according to any one of claims 1 to 3, wherein the (A) metal oxide hollow particles are hollow particles containing (A-1) rutile-type titanium oxide and (A-2) silica. resin composition for
The resin composition for cutting blue light according to claim 4, wherein the content of (A-2) silica in (A) is 0.5% by mass or more and 30% by mass or less.
The resin composition for cutting blue light according to any one of claims 1 to 5, wherein the (B) transparent resin is a curable resin.
A blue light cut film comprising the blue light cut resin composition according to any one of claims 1 to 6.
A blue light blocking layer comprising the blue light blocking resin composition according to any one of claims 1 to 6.
An optical filter having the blue light cut film according to claim 7 or the blue light cut layer according to claim 8.
Eyewear having the blue light cut film according to claim 7 or the blue light cut layer according to claim 8.