JP2021113305A - Resin composition using hollow particle and application of the same - Google Patents

Abstract

To provide a resin composition which is excellent in sedimentation stability while holding a conventional function of light scattering property compared to conventional titanium oxide fine particles, therefore to provide a resin composition which is excellent in light scattering property, sedimentation stability, a refractive index, dielectric property, light weight property, heat insulating property and sound insulation property, and gives a cured film that is suitable for an electric component, in particular, display application.SOLUTION: A resin composition contains (A) rutile-type titanium oxide hollow particles. The resin composition more preferably contains (B) a curable compound, (C) a curing agent, and (D) a solvent.SELECTED DRAWING: None

Description

The present invention relates to a resin composition containing rutile-type hollow titanium oxide particles and its use. More specifically, the present invention relates to a titanium oxide-containing resin composition having excellent sedimentation stability, a cured film exhibiting unique performance in optical properties such as light scattering, and its use.

Hollow particles are widely used as microcapsules containing various functional substances inside the particles, and by utilizing the unique light scattering characteristics of internal pores, they can be used for paper, fibers, leather, glass, metals, etc. It is known that it is also useful as a light scattering agent and a light scattering aid for imparting performance such as brilliance, luster, opacity, and whiteness in the fields of coatings, inks, paints, cosmetics, and the like. Further, since the inside is a hole, it can be expected to be effective as a refractive index adjusting agent, a dielectric constant adjusting agent, a lightweight agent, a sound insulating material, and a heat insulating material.
Among the 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 to be useful as light scattering materials and catalytic materials because of their high refractive index and catalytic activity.

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

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

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

Japanese Unexamined Patent Publication No. 2013-23676 Japanese Unexamined Patent Publication No. 06-330606 Japanese Unexamined Patent Publication No. 05-13809 Japanese Unexamined Patent Publication No. 2010-12786

The resin composition using the conventional hollow particles as described above has a short pot life due to the influence of sedimentation property, and may cause defects in the manufacturing process. In addition, the optical characteristics are not sufficient, and there are restrictions such as not being able to be used for display applications due to insufficient light scattering properties.

As a result of diligent studies, the present inventors have found that a resin composition using rutile-type titanium oxide hollow particles has excellent storage stability and has unique optical properties because of its low sedimentation property.
That is, the present invention relates to the following 1) to 11).
1)
(A) A resin composition containing rutile-type titanium oxide hollow particles.
2)
The resin composition according to 1) above, further containing (B) a curable compound and (C) a curing agent.
3)
The resin composition according to 1) or 2) above, which further contains (D) a solvent.
4)
The resin composition according to any one of 1) to 3) above, wherein the (A) rutile-type titanium oxide hollow particles are hollow particles having rutile-type titanium oxide and silica.
5)
The resin composition according to any one of 1) to 4) above, wherein the primary average particle size of the rutile-type titanium oxide hollow particles is 0.1 to 1.0 μm.
6)
The resin according to any one of 1) to 5) above, wherein the ratio of the hollow diameter A / particle diameter B of the rutile-type titanium oxide hollow particles is 0.3 to 0.95. Composition.
7)
The resin composition according to any one of 1) to 6) above, wherein the rutile-type titanium oxide hollow particles have a spherical shape.
8)
The item according to any one of 1) to 7) above, wherein the (B) curable compound is at least one compound selected from (B-1) thermosetting resin and (B-2) photocurable resin. Resin composition.
9)
The item according to any one of 1) to 8) above, wherein the (C) curing agent is at least one curing agent selected from (C-1) thermosetting agent and (C-2) radical polymerization initiator. Resin composition.
10)
A cured film obtained by curing the resin composition according to any one of 1) to 9) above.
11)
A display device having the cured film according to 11) above.

The following are also preferable as rutile-type titanium oxide and its applications.
12)
Rutile-type titanium oxide hollow particles having an A / B value of 0.1 or more and less than 0.3, where A is the hollow diameter of the hollow particles and B is the particle size of the hollow particles.
13)
The rutile-type titanium oxide hollow particles according to 13) above, wherein the primary particle diameter is 10 nm or more and 1000 nm or less.
14)
The rutile-type titanium oxide hollow particles according to 12) or 13) above, wherein the coefficient of variation of the primary particle size is 10% or less.
15)
The rutile-type titanium oxide hollow particles according to any one of 12) to 14) above, wherein the sphericity is 0.5 or more and 1.0 or less.
16)
The rutile-type titanium oxide hollow particles according to any one of 12) to 15) above, which contain silica.
17)
The rutile-type titanium oxide according to 16) above, wherein the titanium oxide content is 86.0 mol% or more and 99.5 mol% or less, and the silica content is 0.5 mol% or more and 14.0 mol% or less. Hollow particles.
18)
A cosmetic using the rutile-type titanium oxide hollow particles according to any one of 12) to 17) above.
19)
(A) A dispersion containing the rutile-type titanium oxide hollow particles according to any one of the above 12) to 18) and (B) a solvent.
20)
(C) The dispersion liquid according to 19) above, which contains a dispersant.
21)
White ink using the dispersion liquid according to 19) or 20) above.
According to 12) to 21), white has excellent sedimentation stability and particle strength, for example, excellent brilliance and gloss when used as a powder cosmetic, and good hiding property when contained as a colorant. It is possible to provide rutile-type titanium oxide hollow particles from which ink can be obtained.
Hereinafter, Non-Patent Document 1 discloses hollow particles using anatase-type titanium oxide. However, since the anatase type has a photocatalytic function, there is a concern that the composite such as resin may be decomposed by light when it is composited.
[Non-Patent Document 1] SONG, X et al. , Fabrication of Hollow Hybrid Microspheres Coated with Silka / Titania via Sol-Gel Process and Enhanced Photocatalytic Activities, J. Mol. Phys. Chem. C, 2007.05.16, Vol. 111, p. 8180-, ISSN 1932-7447

According to the present invention, it is possible to provide a resin composition having excellent light scattering property, sedimentation stability, refractive index, dielectric property, light weight, heat insulating property, sound insulating property and the like. The resin composition also provides a cured film useful for electronic components, especially for display applications.

[(A) Rutile-type titanium oxide hollow particles]
The resin composition of the present invention contains rutile-type titanium oxide hollow particles as the component (A).
Since rutile-type titanium oxide has a low photocatalytic function and a high refractive index, it is excellent in controlling the reflectance with respect to wavelength. The ratio of rutile-type titanium oxide in titanium oxide is usually 80% to 100%, preferably 85% to 100%, and more preferably 90% to 100%. In this specification, "~" includes the values before and after. The ratio is a value calculated from the X-ray diffraction peak.
Further, the hollow particles are spherical, substantially spherical, uneven, irregularly shaped particles having pores formed inside and the shell formed of the rutile-type titanium oxide, and may be spherical or substantially spherical. It is preferable, and it is more preferable that it is spherical. Further, the pores inside the hollow particles preferably have a high roundness when the pores are regarded as spheres.
In this specification, rutile-type titanium oxide hollow particles may be simply referred to as hollow particles, and rutile-type titanium oxide may be simply referred to as titanium oxide.
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 an electron diffraction image of a single particle 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.

<Silica>
The rutile-type titanium oxide hollow particles used in the resin composition of the present invention preferably contain silica in the titanium oxide portion. The silica may be crystalline or amorphous, but is preferably amorphous. It can be confirmed by a known method that silica is amorphous. As a known method, for example, a method of measuring a diffraction peak derived from a silica crystal (for example, α-SiO _{2) using an X-ray diffractometer or the like can be mentioned.} As used herein, the term "amorphous" means that a clear diffraction peak derived from a crystal does not appear.
When silica is contained, the titanium oxide content is preferably 86.0 mol% or more and 99.5 mol% or less, and more preferably 90.0 mol% or more and 97.5 mol% or less. Further, the hollow particles according to the present embodiment preferably have a silica content of 0.5 mol% or more and 14.0 mol% or less, and more preferably 2.5 mol% or more and 10 mol% or less. .. The content of titanium oxide and silica contained in the hollow particles is calculated assuming that the titanium oxide precursor and silica precursor in producing the hollow particles are converted into titanium oxide and silica at a conversion rate of 100%. When calculating these content rates, round off the second digit after the decimal point and enter up to the first digit after the decimal point.
In the hollow particles, the boundary between the titanium oxide layer having a hollow structure and the silica layer may be a composite oxide.
Further, the silica contained in the hollow particles may be crystalline or amorphous, but is preferably amorphous. It can be confirmed by a known method that silica is amorphous. As a known method, for example, a method of measuring a diffraction peak derived from a silica crystal (for example, α-SiO _{2) using an X-ray diffractometer or the like can be mentioned.} In the present specification, "amorphous" means that a clear diffraction peak derived from a crystal does not appear.

<Hollow diameter and particle diameter parameters A / B>
The rutile-type titanium oxide hollow particles used in the resin composition of the present invention have an A / B value of 0.3 to 0.95, where A is the hollow diameter of the hollow particles and B is the particle diameter of the hollow particles. It is preferable that there is. That is, it has a structure in which rutile-type titanium oxide is a shell and has a hollow inside, which is larger than 5% and less than 70% of the particle size.
The hollow particles according to the present embodiment preferably do not have pores leading from the surface of the particles to the internal pores. Whether or not it has such pores is determined by measuring the amount of adsorption and the amount of desorption with respect to relative pressure using, for example, a pore distribution measuring device (for example, BELSORP-mini II manufactured by Microtrac Bell Co., Ltd.). It can be confirmed by. In the present specification, "having no pores leading to internal vacancies" means that the adsorption / desorption isotherm created from the adsorption amount and the desorption amount is not type IV or V in the IUPAC classification. .. In the IUPAC classification, types II and III are preferable, and type II is more preferable.
The preferable upper limit of the A / B value is 0.9, more preferably 0.85, and particularly preferably 0.8. The lower limit is preferably 0.4, more preferably 0.5, and particularly preferably 0.6. Therefore, 0.6 or more and 0.8 or less is the most preferable range.
The hollow diameter A of the hollow particles and the primary particle diameter B of the hollow particles are the hollow diameter A of 10 hollow structure particles randomly photographed by a transmission electron microscope (TEM) and the primary particles of the hollow particles. It is an arithmetic average value of the diameter B. When the significant figure of the ratio A / B is one digit after the decimal point, the second digit after the decimal point is rounded off. If the significant figures 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 hollow particles may be expressed as an inner diameter.

<Primary particle size of hollow particles>
It is difficult to unconditionally determine the primary particle size of the rutile-type titanium oxide hollow particles used in the resin composition of the present invention because there is an appropriate range depending on the application. From the viewpoint of production, it is usually 10 nm to 1000 nm, preferably 50 nm to 750 nm, more preferably 100 nm to 700 nm, still more preferably 150 nm to 500 nm, and particularly preferably 180 nm to 500 nm. Within such a range, hollow particles having a target structure tend to be stably produced. When a white pigment is used, it is usually 200 nm to 450 nm, preferably 250 nm to 350 nm so that the hiding property is good.

<Coefficient of variation of primary particles>
The rutile-type titanium 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 coefficient of variation of the primary particle size of the hollow particles can be calculated from the following formula.
Coefficient of variation (%) = Standard deviation of primary particle size (nm) / Arithmetic mean particle size (nm)
A smaller coefficient of variation is preferable because it indicates that particles having a 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 small, ideally 0%.

<Spherical degree>
The rutile-type titanium 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.
The sphericity can be measured by a transmission electron microscope (TEM).
That is, it is an arithmetic mean value calculated by using the following formula from the long axis and the area of 10 hollow particles photographed at random. If the significant digit of sphericity is one digit after the decimal point, the second digit after the decimal point is rounded off. If the significant figure of sphericity is two digits after the decimal point, the third digit of the decimal point is rounded off.
Sphericality = (4 x particle area (nm ² )) / (π x (major axis (nm)) ² )
Further, the sphericity may be calculated using the image analysis software Image J.
When the sphericity is in the above range, the dispersibility is improved and the slipperiness to the skin is excellent when used as a powder cosmetic.

<Other configurations of hollow particles>
The rutile-type titanium oxide hollow particles used in the resin composition of the present invention include the above-mentioned silica, for example, Sn, Cd, Fe, Ni, Zn, Mn, Co, Cr, Cu, in addition to the rutile-type titanium oxide. , K, Na, Li, P, S and the like. These elements may be one kind or two or more kinds.

When the rutile type titanium 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 based on the number of moles of titanium in titanium oxide. , Usually 0.1 mol% to 15 mol%, preferably 0.1 mol% to 10 mol%, more preferably 0.1 mol% to 5 mol%. Within such a range, it tends to be easy to obtain hollow particles with less coloring (that is, higher whiteness).

The rutile-type titanium oxide hollow particles used in the resin composition of the present invention may further have a layer of another substance on the surface thereof, if necessary. Examples of other substances include alumina, aluminum hydroxide, zinc oxide, zinc hydroxide, zirconia, organic substances and the like.

<Manufacturing method of hollow particles>
The rutile-type titanium oxide hollow particles used in the resin composition of the present invention include, for example, Xiong Wen (David) Lou, Linden A. et al. Archer and Zichao Yang, Adv. Mater. , 2008, 20, 3987-4019 and the like. However, it is not limited to this manufacturing method.

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

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

<First step>
The first step includes a step of reacting the template particles with the titanium oxide precursor and the silica precursor in the presence of a base in an organic solvent. The silica precursor may be added after the addition of the titanium oxide precursor, or may be added at the same time as the titanium oxide precursor. By 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 the template particles to be the core.

Examples of the template particles include particles selected from polymer particles and inorganic particles. Specific examples thereof include polymer particles obtained by polymerizing at least one monomer selected from (meth) acrylate-based, vinyl-based, styrene-based, and urethane-based; calcium carbonate, iron oxide, cobalt oxide, and the like. Inorganic particles such as manganese oxide, chromium oxide, nickel oxide; Among these, polymer particles are preferable, polymer particles containing styrene as a constituent monomer are more preferable, styrene- (meth) acrylic acid polymer particles are further preferable, and styrene-methacrylic acid polymer particles are particularly preferable.
In addition, 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 is a substance that can be converted into titanium oxide by a chemical or physical method. Among the titanium oxide precursors, titanium alkoxide is preferable. As the titanium alkoxide, titanium tetraalkoxide is preferable, titanium tetra C1-C6 alkoxide is more preferable, and titanium tetrabutoxide is further preferable.

By controlling the amount of titanium oxide precursor added, the thickness of the shell can be controlled. The titanium oxide precursor may be added in an amount required to make the shell to a specific thickness at a time, or may be added in several portions. By adding the titanium oxide precursor in several portions, the thickness of the shell tends to be more uniform.

The silica precursor is not particularly limited as long as it is a substance that can be converted into silica by a chemical or physical method. Among the silica precursors, silane alkoxide is preferred. As the silane alkoxide, silanetetraalkoxide is preferable, silanetetra C1-C4 alkoxide is more preferable, and silanetetraethoxyoxide is further preferable.

Examples of the organic solvent include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, butanol, t-butanol, benzyl alcohol, etc.), and ketone solvents. Solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetyl acetone, etc.), ester solvents (ethyl acetate, methyl acetate, butyl acetate, cellosolve acetate, amyl acetate, etc.), ether solvents (isopropyl ether, methyl cellosolve, etc.) 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 solvent (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), glyme solvent (monoglyme, diglime, etc.), halogen solvent (dichloromethane, chloroform, etc.), amide solvent (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, the concentration of the template particles, the method of adding the base, and the like, the first step can be performed while maintaining a good dispersed state of the reaction solution.

Examples of the base include an inorganic base and an organic base. Examples of the inorganic base 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 the organic base include heteroaromatic ring compounds such as pyridine; alkylamines such as triethylamine (preferably trialkylamines, more preferably tri-C1-C4 alkylamines); hydroxyalkylamines such as triethanolamine (preferably tris). (Hydroxyalkyl) amines, more preferably tri (hydroxy C1-C4 alkylamines)); and the like.

The first step is preferably carried out in an atmosphere of an inert gas 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, the thickness of the shell, and the like, it is difficult to unconditionally determine the reaction time. As a guide, it is usually about 0.1 hour to 10 hours, preferably about 0.5 hour to 7 hours.

When the template particles are polymer particles and their surface potential has the same code as titanium oxide, core / shell particles can also be formed by the following method.
That is, an organic polymer having a sign opposite to the above surface potential (for example, polyethyleneimine) is adsorbed on the surface of the template particles. The core / shell particles can then be formed by depositing or adsorbing titanium oxide fine particles on the surface of the organic polymer and adding titanium oxide precursors as needed. 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 changed to the rutile-type.

In the first step, the reaction is carried out in the state of a dispersion liquid. Therefore, for the purpose of improving the dispersion stability of the dispersion, the first step is preferably performed in the presence of a dispersant. The type of dispersant is not particularly limited as long as it does not interfere with the formation of the shell. 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 Big Chemie Japan Co., Ltd .; Solspers series; Ajinomoto Fine Techno Co., Ltd.'s Ajispar series; Kusumoto Kasei Co., Ltd.'s Disparon series; etc.

<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 preferable. When the template particles are polymer particles, examples of the solvent used in the second step include 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 an aqueous solution of an acid such as dilute hydrochloric acid, dilute nitric acid, or dilute sulfuric acid.

<Third step>
Examples of the third step include a step of obtaining hollow particles by firing the shell particles obtained in the second step. Normally, firing can be performed in an atmosphere of a gas selected from one or more types such as air, nitrogen, argon, hydrogen, and ammonia, but in order to obtain single crystal titanium oxide, firing is performed in an air atmosphere. It is preferable to do so. In addition, in this specification, "air" is a gas constituting the lowest layer of the earth's atmosphere, and means a gas obtained in a normal environment in which human beings live.

Since the firing temperature in the third step changes depending on the material of the hollow particles and the like, it is difficult to unconditionally determine it. As a guide, it is usually 600 ° C. to 1500 ° C. or lower, preferably 650 ° C. to 1400 ° C., more preferably 700 ° C. to 1300 ° C., and further preferably about 750 ° C. to 1200 ° C.
Since the firing time of the third step changes depending on the firing temperature and the like, it is difficult to unconditionally determine it. As a guide, it is usually 0.5 hours to several tens of hours, preferably about 1 hour to 10 hours.

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

The hollow particles obtained in the third step may contain particles of by-products having a non-uniform shape. The proportion of by-product particles is usually 10% or less, preferably 5% or less. By precisely controlling the synthesis conditions and the like, it is possible to suppress the formation of particles of by-products. The content of by-products can be calculated from the number of non-uniformly shaped particles out of 100 hollow particles randomly photographed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). can.

The resin composition of the present invention preferably contains (A) the above-mentioned rutile-type titanium oxide hollow particles, (B) a curable compound, and (C) a curing agent.
The content of the (A) rutile-type titanium 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 content thereof differs depending on whether the target resin composition is a solid resin composition or a liquid resin composition.
For example, in the case of a solid resin composition, the upper limit of the content is more preferably 50% by mass, and more preferably 40% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass. % Is particularly preferable. Further, as the lower limit, 0.2% by mass is more preferable, and 0.5% by mass, 1% by mass, 2% by mass, and 3% by mass are more preferable, and 5% by mass is particularly preferable. Therefore, the most preferable content of the (A) rutile-type titanium oxide hollow particles is 5% by mass or more and 10% by mass or less.
Further, for example, in the case of a liquid cosmetic, the upper limit of the content is more preferably 40% by mass, more preferably 30% by mass, 20% by mass, 15% by mass, and particularly preferably 10% by mass. Further, as the lower limit, 0.2% by mass is more preferable, and 0.5% by mass, 1% by mass, 2% by mass, and 3% by mass are more preferable, and 5% by mass is particularly preferable. Therefore, the most preferable content of the (A) rutile-type titanium oxide hollow particles is 5% by mass or more and 10% by mass or less.

[(B) Curable compound]
Examples of the (B) curable compound that can be used in the present invention include (B-1) thermosetting compounds and (B-2) photocurable compounds.
[(B-1) Thermosetting compound]
Examples of the thermosetting compound include curable compounds having a cyclic ether such as an epoxy group and an oxetanyl group.
The thermosetting compound having the cyclic ether is not particularly limited, and examples thereof include an epoxy resin (aliphatic epoxy resin containing an alicyclic epoxy resin or an aromatic epoxy resin), an oxetane resin, and a furan resin. Of these, epoxy resins (which may contain an aliphatic ring, for example, an aliphatic ring having 3 to 12 carbon atoms) and an oxetane resin are preferable from the viewpoint of reaction rate and versatility. The epoxy resin is not particularly limited, and for example, novolak type such as phenol novolac type, cresol novolac type, biphenyl novolac type, trisphenol novolac type, dicyclopentadiene novolac type; bisphenol A type, bisphenol F type, 2, 2 '-Diallyl bisphenol A type, hydrogenated bisphenol type, polyoxypropylene bisphenol A type and other bisphenol types can be mentioned. In addition, glycidylamine and the like can also be mentioned.
Examples of commercially available epoxy resins include Epicron (registered trademark) N-740, N-770, and N-775 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.) as phenol novolac type epoxy resins. Examples thereof include Epicoat (registered trademark) 152 and Epicoat (registered trademark) 154 (all manufactured by Japan Epoxy Resin Co., Ltd.). Examples of the cresol novolac type include Epicron® N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP, and N-672-EXP (above). , All manufactured by Dainippon Ink and Chemicals Co., Ltd.); Biphenylnovolak type, for example, NC-3000P (manufactured by Nippon Kayakusha); Trisphenol novolak type, for example, EP1032S50, EP1032H60 (all of which are Japan Epoxy resin Co., Ltd.); Dicyclopentadiene novolac type includes, 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. Examples thereof include Epicoat (registered trademark) 828, Epicoat (registered trademark) 834, Epicoat 1001, Epicoat (registered trademark) 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicron (registered trademark) 850, and Epicron (registered trademark). Registered trademark) 860, Epicron (registered trademark) 4055 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Commercially available bisphenol F type epoxy compounds include, for example, Epicoat (registered trademark) 807 (Japan Epoxy Resin Co., Ltd.) Epoxy (registered trademark) 830 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); 2,2'-diallyl bisphenol A type includes, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); hydrogenated bisphenol Examples of the type include ST-5080 (manufactured by Toto Kasei Co., Ltd.); and examples of the polyoxypropylene bisphenol A type include EP-4000 and EP-4005 (all manufactured by Asahi Denka Kogyo Co., Ltd.). Be done.
Commercially available products of the above oxetane compounds include, for example, Etanacol (registered trademark) EHO, Etanacol (registered trademark) OXBP, Etanacol (registered trademark) OXTP, and Etanacol (registered trademark) OXMA (all manufactured by Ube Industries, Ltd.). Can be mentioned. The alicyclic epoxy compound is not particularly limited, and for example, celoxide (registered trademark) 2021, celoxide (registered trademark) 2080, celoxide (registered trademark) 3000 (all of which are manufactured by Daicel UCB Co., Ltd.). And so on. These curable compounds having a cyclic ether group may be used alone or in combination of two or more.

[(B-2) Photocurable compound]
Examples of the photocurable compound include 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, for example, a (meth) acrylate compound is preferable from the viewpoint of reactivity and versatility. In the present specification, terms such as "(meth) acryloyl" mean "acryloyl" or "methacryloyl", and for example, "(meth) acrylate" means "acrylate" or "methacrylate".
Examples of the resin having a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, and acryloyl. Half ester, which is a reaction product of morpholine, hydroxyl group-containing (meth) acrylate and acid anhydride of polycarboxylic acid compound, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate. , Trimethylol propanepolyethoxytri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate (for example, KAYARAD manufactured by Nippon Kayaku Co., Ltd.) (Registered Trademarks) HX-220, HX-620, etc.), Pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of the reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate (for example, Japan). KAYARAD (registered trademark) DPHA, etc. manufactured by Kayaku Co., Ltd.), (meth) acrylate compounds such as epoxy (meth) acrylate, which is a reaction product of mono or polyglycidyl compound and (meth) acrylic acid, can be mentioned.
The glycidyl compound used for epoxy (meth) acrylate, which is a reaction product of mono or polyglycidyl compound and (meth) acrylic acid, is not particularly limited, and is, for example, bisphenol A, bisphenol F, bisphenol S, 4,4'-. 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 with diisopropyridene skeleton, 1,1-di-4 -Pharmons having a fluorene skeleton such as hydroxyphenylfluorene, phenolized polybutadiene, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol Examples thereof include glycidyl etherified products of polyphenols such as A.
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 of an equivalent amount of (meth) acrylic acid. This synthetic reaction can be carried out by a generally known method. For example, resorcindiglycidyl ether with the equivalent amount of (meth) acrylic acid, catalysts (eg, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibin, etc.) and polymerization inhibitors (eg, methquinone, etc.) Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) are added together, and the esterification reaction is carried out at, for example, 80 to 110 ° C. The (meth) acrylicized resorcinol diglycidyl ether thus obtained is a resin having a radically polymerizable (meth) acryloyl group.

As the curable compound (B), a thermosetting resin or a photocurable resin is preferable, and a photocurable resin is more preferable.
Further, it is particularly preferable that the photocurable resin has three or more (meth) acryloyl groups in the molecule.
Examples of the photocurable resin having 3 or more (meth) cryloyl groups and polar functional groups in the molecule include pentaeryth little triacrylate (KAYARAD PET-30 manufactured by Nippon Kayaku), dipentaeryth little pentaacrylate and di. Mixture of pentaeryth little hexaacrylate (KAYARAD DPHA Nippon Kayaku), 2-hydroxy-3-acryloyloxypropyl methacrylate (701A Shin-Nakamura Chemical), ethoxylated isocyanuric acid triacrylate (A-9300 Shin-Nakamura Chemical) , Ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (A-9300-1CL Shin-Nakamura Kagaku) and other (meth) acrylate monomer compounds, bisphenol A type epoxy acrylate (R-115F, R-130, R) -381 etc. Nippon Kayaku), bisphenol F type epoxy acrylate (ZFA-266H Nihon Kayaku), acid modified epoxy acrylate (ZAR series, ZCR series Nihon Kayaku) and other epoxy acrylate resins, polyester urethane acrylate ( UX3204, UX-4101, UXT-6100 manufactured by Nippon Kayaku), mixed urethane acrylate (UX-6101, UX-8101 manufactured by Nihon Kayaku), polyether urethane acrylate (UX-937, UXF-4001-M35 made in Japan) (Yakuhin), ester-based urethane acrylates (DPHA-40H, UX-5000, UX-5102D-M20, UX-5103D, UX-5005 Nippon Kayaku) and other urethane acrylate resins can be mentioned.
The photocurable resin having 3 or more (meth) acryloyl groups in the molecule is more preferably 3 or more and 10 or less (meth) acryloyl groups, and further preferably 4 or more and 8 or less (meth). This is the case when it has 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) Hardener]
The resin composition of the present invention preferably contains a curing agent as (C). In particular, when (B) a curable compound is used, (C) a curing agent is used in combination. In some cases, a curing agent and an initiator may be distinguished, but in the present specification, both are included and described as (C) curing agent.

When the (B-1) thermosetting compound is used as the (B) curable compound, it is preferable that the (C-1) thermosetting agent is used in combination as the component (C). However, when the (B-1) thermosetting compound is a thermosetting compound having a cyclic ether, a photocation initiator or a photoanion initiator that generates a cation or anion by light can also be preferably used.
(C-1) The thermal curing agent is one that reacts nucleophilically by an unshared electron pair or an anion in the molecule, and is, for example, an amine-based curing agent (hereinafter, also referred to as amines) or a hydrazide-based curing agent. (Hereinafter referred to as hydrazides), imidazole-based curing agents (hereinafter also referred to as imidazoles), polyamide resins, dicyandiamides, isocyanates, thiol-based curing agents (thiols), phenol-based curing agents (phenols) and the like can be mentioned. .. However, it is not limited to these.
Examples of amines include aliphatic chain amines, aliphatic cyclic amines, aromatic amines, modified amines (amine adduct, ketimine, etc.) and the like. Further, any of primary amine, secondary amine, tertiary amine and quaternary amine may be used, but from the viewpoint of reactivity, primary or secondary amine is preferable.
Specifically, as amines, for example, diaminodiphenylmethane, diaminodiphenylsulphon, 4,4'-diamino-3,3'-dimethyldiphenylmethane, diaminodiphenyl ether, diethylmethylbenzenediamine, 2-methyl-4,6-bis (methylthio). ) -1,3-benzenediamine, bisaniline, diethyltoluenediamine, aromatic amines such as diethylthiotoludiamine, N, N'-bis (sec-butylamino) diphenylmethane, methylamine, dimethylamine, trimethylamine, ethylamine, Examples thereof include aliphatic amines such as diethylamine, triethylamine, ethylenediamine, tetramethylethylenediamine, hexamethylenediamine, norbornandiamine, polyetheramine, triethylenetetramine and tetraethylenepentamine, and modified amines. Particularly preferably, diethylmethylbenzenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, diethyltoluenediamine can be mentioned.
As the hydrazides, an organic acid hydrazide compound is particularly preferably used. For example, the aromatic hydrazides salicylate hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzenetrihydrazide, 1,4,5,8. -Tetrahydrazide naphthoate, tetrahydrazide pyromellitic acid, etc. can be mentioned. In the case of an aliphatic hydrazide compound, for example, formhydrazide, acetohydrazide, propionate hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutarate dihydrazide, adipic acid dihydrazide, pimelliate dihydrazide, sebacic acid dihydrazide. 1,4-Cyclohexanedihydrazide, tartrate dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebis semi-carbazide, citrate trihydrazide, nitriloacetate trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis ( Tris (1-hydrazinocarbonylmethyl), a dihydrazide compound having a hydrandin skeleton such as hydradinocarbonoethyl) -5-isopropylhydranthin, preferably a valine hydrantin skeleton (a skeleton in which the carbon atom of the hydrandin ring is replaced with an isopropyl group). Isocyanurate, Tris (2-hydrazinocarbonylethyl) isocyanurate, Tris (1-hydrazinocarbonylethyl) isocyanurate, Tris (3-hydrazinocarbonylpropyl) isocyanurate, Bis (2-hydrazinocarbonylethyl) isocyanurate Etc. can be given. From the balance of curing reactivity and potential, preferred isiophthalic acid dihydrazide, malonic acid dihydrazide, adipate dihydrazide, tris (hydrazinocarbonylmethyl) isocyanurate, tris (1-hydrazinocarbonylethyl) isocyanurate, tris (2-). Hydradinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, and particularly preferably tris (2-hydrazinocarbonylethyl) isocyanurate.
Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl-4-methyl imidazole, 1-benzyl-2-phenyl imidazole, 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')) 1')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 addition , 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 calends MT PE1, BD1, NR1, trimethylolpropane tris (3-mercaptobutyrate), and trimethylolethane ethanetris (3-mercaptobutyrate) (all manufactured by Showa Denko KK). Can be done. The thiol-based curing agent is a curing agent having at least one thiol group (SH) in the molecule.
Examples of the phenols include phenol novolacs, bisphenol A, bisphenol S and the like obtained by subjecting phenol (which may have various substituents) to a condensation reaction of formalin under an acid catalyst.

When a thermosetting agent is used, a thermosetting accelerator may be used in combination. Examples of the curing accelerator include phenols, organic acids, phosphines, imidazole and the like as the curing accelerator.
Examples of the organic acid include an organic carboxylic acid and an organic phosphoric acid, and an organic carboxylic acid is preferable. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenonetetracarboxylic acid, and flangecarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, and 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, tetraphenylphosphonium tetraphenylborate and the like.
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-methylimidazole isocyanuric acid 2: 3 adduct , 2-Phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxy Examples thereof include methylimidazole.

[(C-2) Photoinitiator]
When the (B-2) photocurable compound is used as the (B) curable compound, it is preferable that the (C-2) photoinitiator is used in combination as the component (C). However, since the (B-2) photocurable compound has a functional group that undergoes a chain polymerization reaction with a radical such as a double bond, for example, the use of a thermal radical initiator that generates a radical by heat is excluded. is not it.
(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 by irradiation with ultraviolet rays or visible light and initiates a chain polymerization reaction, but is not particularly limited, for example, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, diethylthioxanthone, benzophenone, 2-ethyl. Anthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, camphorquinone , 9-Fluorenone, diphenyldisulfide 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), Sakeall ^RTM Z, BZ, BEE, BIP, BBI (all manufactured by Seiko Kagaku Co., Ltd.) and the like can be mentioned.
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 more preferably 1000 or more and 7500 (m). It is particularly preferable that the content is mL / g · cm) or less. The molar extinction coefficient was measured using methanol or acetonitrile as a solvent.
Photopolymerization initiators having a molar extinction coefficient (ε) of 100 or more and 10000 (mL / g · cm) or less at 365 nm are IRGACURE ^RTM 651 (ε = 360 ^{mL / g · cm in methanol) and 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 = 4700 mL / g · cm in acetonitrile), IRGACURE ^RTM OXE-01 (ε = 7000 mL / g · cm in ^{acetonitrile), IRGACURE RTM} OXE-02 (ε = 7700 mL / g · in acetonitrile) cm) and the like, but are not limited to these.
When a photoradical 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 preferable 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.
The lower limit is preferably 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) When a thermal radical polymerization initiator is used for the photocurable compound, the thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction. , Organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, benzopinacol and the like, and benzopinacol is preferably used. For example, as organic peroxides, Kayamec (registered trademark) A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Cadox B-40ES, Parkadox 14, 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, Parkadox 16, Kayacarbon (registered trademark) BIC-75, AIC-75 (manufactured by Chemical Axo Co., Ltd.), Permec (registered trademark) N, H, S, F, D, G, Perhexa (registered trademark) H, HC , TMH, C, V, 22, MC, Percure® AH, AL, HB, Perbutyl® H, C, ND, L, Park Mill® H, D, Parloyl® IB , IPP, Per Octa (registered trademark) ND (manufactured by Nichiyu Co., Ltd.), etc. are available as commercial products. As the azo compound, VA-044, V-070, VPE-0201, VSP-1001 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are available as commercial products.
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 preferable 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.
The lower limit is preferably 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 of the content in the resin composition is 1.5 parts by mass or more and 3 parts by mass or less.

[(D) Solvent]
The resin composition of the present invention may contain the solvent (D).
The solvent that can be used may be water-soluble or water-insoluble.
Examples of the water-insoluble solvent include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, acetyl acetone, 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, etc.) Ether, etc.), Glycol ester-based solvent (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), Glyme-based solvent (monoglyme, diglyme, etc.), halogen-based solvent (dichloromethane, chloroform, etc.), tetrahydrofuran Can be mentioned.
Examples of the water-soluble solvent include C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, N, N-dimethylacetamide and the like. Carboxyl amides; lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2-one, 1,3-dimethylhexahydropyrimido- Cyclic ureas such as 2-one; ketones or keto alcohols such as acetone, 2-methyl-2-hydroxypentane-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, di C2-C6 diols such as propylene glycol, polyethylene glycols with molecular weights of 400, 800, 1540 or higher, polypropylene glycols, thiodiglycols, dithiodiglycols, or mono-, oligo, or polyalkylene glycols having C2-C6 alkylene units. Alternatively, thioglycol; polyol (triol) such as glycerin, diglycerin, hexane-1,2,6-triol, trimethylolpropane, etc .; dimethylsulfoxide; 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 Nate, ethylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glyco Lumonomethyl 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; and the like can be mentioned.

The above-mentioned water-soluble organic solvent also contains a substance that is solid at room temperature, such as trimethylolpropane. However, the substance or the like exhibits water solubility even if it is a solid, and the aqueous solution containing the substance or the like exhibits the same properties as the water-soluble organic solvent, and can be used with the expectation of the same effect. Therefore, in the present specification, for convenience, even such a solid substance is included in the category of water-soluble organic solvent as long as it can be used with the expectation of the same effect as described above.

Preferred water-soluble organic solvents are isopropanol, glycerin, mono, di, triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, trimethylolpropane, and the like. And butylcarbitol, more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and butylcarbitol. These water-soluble organic solvents are used alone or in combination.
The content of the solvent (B) is preferably 1 to 90% by mass with respect to the total mass of the resin composition of the present invention. In the resin composition using the above-mentioned (A) rutile-type hollow titanium oxide particles, (B) a curable compound, (C) a curing agent and other components are used in an appropriate blending amount, and if there is a balance, there is a balance. The rest may be the solvent (D).
As the upper limit of the content rate, 80% by mass is more preferable, 60% by mass is further preferable, and 40% by mass is particularly preferable. Further, as the lower limit, 10% by mass is more preferable, 20% by mass is further preferable, and 30% by mass is particularly preferable. Therefore, the most preferable content of the solvent (B) is 30% by mass or more and 40% by mass or less.

<Other ingredients>
In addition to the above components (A) to (D), the resin composition of the present invention contains a dispersant, a thermoplastic resin, a surfactant, a powder, a water-soluble polymer, an ultraviolet absorber, a metal ion sequestering agent, an amino acid, and a high content. A molecular emulsion, a pH adjuster, an antioxidant, an antioxidant aid and the like can be appropriately contained as needed.

<Dispersant>
Dispersants include fatty acid salt (soap), α-sulfo fatty acid ester salt (MES), alkylbenzene sulfonate (ABS), linear alkylbenzene sulfonate (LAS), alkyl sulfate (AS), alkyl ether sulfate. Low molecular weight anionic (anionic) compounds such as salt (AES) and alkylsulfate triethanol, low molecular weight such as fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkyl phenyl ether (APE), sorbitol and sorbitan. Low molecular weight cationic compounds such as nonionic compounds, alkyltrimethylammonium salts, dialkyldimethylammonium chlorides and alkylpyridinium chlorides, low molecular weight amphoteric compounds such as alkylcarboxybetaine, sulfobetaine and lecithin, and naphthalene sulfonic acids. Formalin condensate of salt, polystyrene sulfonic acid salt, polyacrylic acid salt, copolymer salt of vinyl compound and carboxylic acid-based monomer, high molecular weight aqueous dispersant typified by carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid Typical examples are high molecular weight non-aqueous dispersants such as partially alkyl esters and polyalkylene polyamines, and high molecular weight cationic dispersants such as polyethyleneimines and aminoalkyl methacrylate copolymers, which are preferably applied to the particles of the present invention. If it is a thing, the thing having a structure other than the form as illustrated here is not excluded.

As the dispersant to be added, the following are known as specific names. Floren DOPA-15B, Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solplus AX5, Solplus TX5, Solspurth 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 54000, Solsix 250, (manufactured by Japan Loubrizor Co., Ltd.), EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA4060, EFKA4080, EFKA4080, EFKA4080 EFKA4402, EFKA4403, EFKA4300, EFKA4320, EFKA4330, EFKA4340, EFKA6220, EFKA6225, EFKA6700, EFKA6780, EFKA6782, EFKA6780 -12 (Ajinomoto Fine-Techno Co., Ltd.), TEXAPHOR-UV21, TEXAPHOR-UV61 (manufactured by Cognis Japan Ltd.), 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, Di sperBYK2155, DisperBYK2164, BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, BYK330, BYK340, BYK350, BYK377, BYK378, BYK350, BYK377, BYK378, BYK350, BYK377, BYK378, BYK31 , Disparon 1860, Disparon 1934, Disparon DA-400N, Disparon DA-703-50, Disparon DA-725, Disparon DA-705, Disparon DA-7301, Disparon DN-900, Disparon NS-5210, Disparon NVI-8514L, Hip Rad ED-152, Hiplard ED-216, Hiplard ED-251, Hiplard ED-360 (Kusumoto Kasei Co., Ltd.), FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX -710LL, FTX-750LL, Futagent 212P, Futagent 220P, Futagent 222F, Futagent 228P, Futagent 245F, Futagent 245P, Futagent 250, Futagent 251, Futagent 710FM, Futagent 730FM, Futagent 730LL , Futergent 730LS, Futergent 750DM, Futergent 750FM (manufactured by Neos Co., Ltd.), AS-1100, AS-1800, AS-2000 (manufactured by Toa Synthetic Co., Ltd.), Kaosera 2000, Kaosera 2100, KDH-154, MX- 2045L, Homogenol L-18, Homogenol L-95, Leodor SP-010V, Leodor SP-030V, Leodor SP-L10, Leodor SP-P10 (manufactured by Kao Co., Ltd.), Evan U103, Cyanol DC902B, Neugen EA-167, Bry Surf A219B, Brisurf AL (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Megafuck F-477, Megafuck 480SF, Megafuck F-482, (manufactured by DIC Co., Ltd.), Silface SAG503A, Dynol 604 (Nisshin Kagaku Kogyo) SN Spurs 2180, SN Spurs 2190, SN Leveler S-906 (manufactured by Sannopco Co., Ltd.), S-386, S-420 (AGC Seimi Chemical Co., Ltd.) (Made by a company) can be exemplified.

<Thermoplastic resin>
Examples of the thermoplastic resin 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, ethyl ethylene acrylate copolymer, acrylonitrile / styrene resin, acrylonitrile / chlorinated polystyrene / styrene copolymer resin, acrylonitrile / acrylic rubber / styrene copolymer resin, acrylonitrile / butadiene -Steryl copolymer resin, acrylonitrile / EPDM / styrene copolymer resin, silicone rubber / acrylonitrile / styrene copolymer resin, cellulose acetate / butyrate resin, cellulose acetate resin, methacryl resin, ethylene / methyl methacrylate copolymer resin, ethylene / ethyl acrylate Resin, vinyl chloride resin, chlorinated polyethylene resin, polytetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoride ethylene / perfluoroalkyl vinyl ether copolymer resin, tetrafluoride ethylene / ethylene Copolymer resin, polytrifluorinated ethylene chloride resin, polyfluorinated vinylidene 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, ultrahigh 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, polyether ether ketone resin, liquid crystal polymer, polytetrafluoroethylene resin, polyfluoroalkoxy resin, polyetherimide resin, polysulfone resin, polyketone resin, thermoplastic polyimide resin, polyamideimide resin, polyallylate resin, polysulfon Examples thereof include, but are not limited to, resins, polyether sulfone resins, biodegradable resins, and biomass resins. Further, it may be a mixture of two or more of these resins.

<Surfactant>
Examples of the surfactant include anionic surfactants, cationic surfactants, amphoteric surfactants, lipophilic nonionic surfactants, hydrophilic nonionic surfactants and the like. 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 the anionic surfactant include fatty acid sulphates (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, sodium lauryl sulfate, etc.). , POE-sodium lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (eg, sodium lauroyl sarcosin, etc.); higher fatty acid amide sulfonate (eg, N-stearoyl-N-methyltaurine sodium, N) -Millistoyl-N-methyl taurine sodium, coconut oil fatty acid methyl taurid sodium, lauryl methyl taurid sodium, etc.); Phosphate ester salts (POE-oleyl ether phosphate sodium, POE-stearyl ether phosphoric acid, etc.); (For example, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); Triethanolamine sulfonic acid, linear dodecylbenzene sulfonic acid, etc.); Higher fatty acid ester sulfate ester salt (for example, cured coconut oil fatty acid sodium glycerin sulfate, etc.); N-acylglutamate (for example, monosodium N-lauroyl glutamate, N- Disodium stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); Sulfated oil (eg, funnel oil, etc.); POE-alkyl ether carboxylic acid; POE-alkylallyl ether carboxylic acid salt; α-olefin sulfonate Higher fatty acid ester sulfonate; Secondary alcohol sulfate ester salt; Higher fatty acid alkylolamide sulfate ester salt; Sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartate ditriethanolamine; Sodium caseinate and the like can be used. ..
(Cationic surfactant)
Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium chloride dialkyldimethylammonium salts; Polychloride (N, N'-dimethyl-3,5-methylenepiperidinium); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkylmoriphonium salt; POE-alkylamine; Examples thereof include alkylamine salts; polyamine fatty acid derivatives; ammonium alcohol fatty acid derivatives; benzalconium chloride; benzethonium chloride and the like.
(Amphoteric surfactant)
Syl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazolin sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyroxy disodium salt, etc.); Betaine-based surfactant (eg, betaine-based surfactant) , 2-Heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, sulfobetaine, etc.) and the like.
(Lipophilic nonionic surfactant)
Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, and sorbitan. Trioleate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.); , Α, α'-Glycerin pyroglutamate oleate, glycerin malic acid monostearate, etc.); propylene glycol fatty acid ester (for example, propylene glycol monostearate, etc.); cured castor oil derivative; glycerin alkyl ether and the like.
(Hydrophilic nonionic surfactant)
Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE-Solbit fatty acid esters (eg, POE-Solbit monolaurate, POE-Solbit monooleate, POE-Solbit pentaoleate, POE-Solbit monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerin mono) POE-monooleates such as stearate, POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.; POE-fatty acid esters (eg, POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.); POE- Alkyl ethers (eg POE-lauryl ethers, POE-oleyl ethers, POE-stearyl ethers, POE-behenyl ethers, POE-2-octyldodecyl ethers, POE-cholestanol ethers, etc.); Pluronic® type (eg, registered trademarks). Pluronic (registered trademark), etc.); POE / POP-alkyl ether (eg, POE / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrous lanolin, etc. POE / POP-glycerin ether, etc.); Tetra POE / tetra POP-ethylenediamine condensate (eg, Tetronic, etc.); Hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-cured castor oil maleic acid, etc.); POE-mituro lanolin derivative (eg, POE-Sorbit Mitsurou, etc.); Alcanolamide (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid Examples include ester; alkylethoxydimethylamine oxide; trioleyl phosphate and the like.
The content of the surfactant is 0 to 20% by mass, preferably 5 to 15% by mass, based on the total mass of the dispersion liquid of the present invention.

<Powder>
As the powder, if it is used in a normal resin composition in addition to the component (A) rutile-type titanium oxide hollow particles, its shape (spherical, needle-like, plate-like, etc.) and particle size (smoke-like, fumes-like, etc.) It can be used regardless of the particle structure (porous, non-porous, etc.) (fine particles, pigment grade, etc.), and for example, one or more of the following can be used. As inorganic powders, for example, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, synthetic mica, mica, kaolin, sericite, white mica, synthetic mica, gold mica, red mica, black mica , Lithia mica, silicic acid, silicic anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hygilite, montmorillonite , Zeolite, ceramics powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, etc .; as organic powder, for example, polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, Polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethylmethacrylate powder, cellulose powder, silk powder, nylon powder, 12 nylon powder, 6 nylon powder, styrene / acrylic acid copolymer powder, divinylbenzene / styrene copolymer powder, Vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicon resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, lauroyl lysine, etc .; 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 black 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, inorganic blue pigments such as dark blue and ultramarine, raked tar pigments, natural Laked dyes, composite powders obtained by combining these powders, etc .; as pearl pigments, for example, titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated Talk, fish scale foil, titanium oxide coated colored mica, etc .; as a metal powder pigment, for example, aluminum powder, copper powder, stainless powder, etc .; as a tar pigment, for example. Red 3, Red 104, Red 106, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 227, Red 228, Red 230, Red 401, Red 505, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Yellow 204, Yellow 401, Blue 1, Blue 2, Blue 201, Blue 404, Green 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, etc .; And so on. It should be noted that these powders may be composited, or a powder whose surface has been surface-treated with an oil agent, silicone, a fluorine compound, or the like may be used.

<Water-soluble polymer>
As the water-soluble polymer, either natural or synthetic can be used, and it is also possible to use them in combination.
Natural water-soluble polymers include, for example, plant-based polymers (eg, arabic gum, tragacanth gum, galactan, guagam, carob gum, karaya gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassaw extract), starch. (Rice, corn, potato, wheat), glycyrrhizinic acid); Micromolecular macromolecules (eg, xanthan gum, dextran, succinoglucan, burran, etc.); Animal macromolecules (eg, collagen, casein, albumin, gelatin, etc.), etc. Can be mentioned.
Examples of the synthetic water-soluble polymer include starch-based polymers (for example, carboxymethyl starch, methyl hydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, etc.). Hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.); alginic acid-based polymers (eg, sodium alginate, propylene glycol alginate, etc.), vinyl-based polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, etc.) Polyvinylpyrrolidone, carboxyvinyl polymer, etc.); Polyoxyethylene polymer (eg, polyethylene glycol 20,000, 40,000, 60,000 polyoxyethylene polyoxypropylene copolymer, etc.); Acrylic polymer (eg, polyethylene glycol 20,000, 40,000, 60,000, etc.); , Polyacrylate sodium, polyethyl acrylate, polyacrylamide, etc.); Polyethyleneimine; Cationic polymer and the like.

<UV absorber>
Examples of the ultraviolet absorber include benzoic acid-based ultraviolet absorbers (for example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxyPABA ethyl ester). , N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); Anthranilic acid-based ultraviolet absorber (for example, homomentyl-N-acetylanthranilate, etc.); Salicylic acid-based UV absorbers (eg, amylsalicylate, menthylsalicylate, homomentylsalicylate, octyl salicylate, phenylsalicylate, benzyl salicylate, p-isopropanol phenylsalicylate, etc.); -4-Isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy Synnamete, 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, glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate, etc.; benzophenone-based ultraviolet absorbers (for example, 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-campayl, 3 -Benzylidene-d, l-Phenyl; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) Benzotriazole; 2- (2'-hydroxy-5-methylphenylbenzotriazole;dibenzalazine;dianisoilmethane;4-methoxy-4'-t-butyldibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) ) -3-Pentan-2-one, dimorpholinopyridadino; 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 can be mentioned.

<Sequestrant>
Examples of the metal ion sequestering agent 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>
Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of the amino acid derivative include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.

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

<Polymer emulsion>
Examples of the polymer emulsion include an acrylic resin emulsion, an ethyl polyacrylate emulsion, an acrylic resin solution, a polyacrylic alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

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

<Antioxidant>
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

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

[Use]
The resin composition of the present invention is very useful as, for example, a member for a light emitting device, a film for light scattering, a quantum dot color resist, a light-shielding resist, an adhesive for electronic parts, and the like.
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 color by adjusting the particle size and the hollow diameter of the hollow structure particles, so that efficient light emission can be achieved. It becomes a member for the device. 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 rutile-type titanium 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 multiplely scattering the light emitted from the light source, and can increase the emission intensity, and are usually used. It is useful because it has better sedimentation stability than the titanium oxide particles of.
The light-shielding resist is useful as a light-shielding partition agent for micro LEDs and the like because it efficiently blocks light by multiple scattering by hollow particles in the resin composition of the present invention.

[Cured film]
Among the above applications, a cured film obtained by curing the resin composition of the present invention is very useful in the application used as a film. Examples of the method for producing this cured film include comma coaters, spray coaters, roll coaters, knife coaters, bar coaters, spin coaters, die coaters, microgravure coaters, screen printing, dispensers, curtain coaters, dip coaters, inkjets, and laminates. After coating by a transfer method or the like, it is photo-cured by irradiating it with ultraviolet rays of about ^{100 to 10,000 mJ / cm 2} , more preferably about 1000 to 6000 mJ / cm ^{2, or 50 to 200 ° C., more preferably 80.} It can be produced by thermosetting at about 130 ° C. for 0.1 hour to 5 hours, more preferably about 0.5 to 2 hours, or by using the above photocuring and thermosetting in combination.

[Manufacturing method of resin composition]
As an example of the method for obtaining the resin composition of the present invention, there is the following method. First, the component (B), the component (D), and other components used as necessary are mixed and dissolved. If necessary, it may be melted by heating. Next, the components (A) and (C) are added, and the mixture is uniformly mixed by a known mixing device such as a 3-roll, sand mill, ball mill or the like, and filtered through a metal mesh to produce the resin composition of the present invention. can do.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. 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, when the amount of the target substance could not be obtained by one synthesis operation or the like, the synthesis operation or the like was repeated until the amount of the target substance was obtained.
The primary particle diameter of the hollow structure particles, the inner diameter of the hollow structure, and the collapsed state after the production of the hollow structure particles were measured using a transmission electron microscope (JEM-2800, manufactured by JEOL Ltd.).
The content of rutile-type titanium oxide was calculated according to the following formula (1) using a powder X-ray diffractometer (X'Pert PRO manufactured by Spectris Co., Ltd.).

The abbreviations and the like in the following formula (1) have the following meanings.
F _R: the content of the rutile type titanium oxide (wt%)
I _A (101): the intensity of the measured powder X-ray diffractometer anatase crystal (101) plane _I R (110): the intensity of the (110) plane of the measured rutile crystals by X-ray powder diffractometer

[Equation 1]

[Preparation of ethanol dispersion (dispersion 1) of template particles]
21 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. The primary particle size of the obtained template particles was 237 nm. The dispersion liquid 1 was prepared by adding ethanol while concentrating the aqueous dispersion liquid of the template particles with an evaporator and replacing the water with ethanol. The content of the template particles in the dispersion liquid 1 was 9% by mass.

[Synthesis Example 1]
(Step 1: Step of obtaining core / shell particles)
20 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 1 (5 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 3 g of titanium tetrabutoxide, 0.1 g of tetraethyl orthosilicate, and 3 g of a 1% potassium hydroxide aqueous solution were added in 3 portions every 0.5 hours, and the mixture was reacted at 10 ° C. for 4 hours to form core /. A liquid containing shell particles was obtained. The obtained 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 2.0 g of the target core / shell particles. rice field.

(Step 2: A step of firing core / shell particles to remove template particles and obtain hollow particles)
2.0 g of the core / shell particles obtained in step 1 was placed on a ceramic board, set in a firing furnace, and fired at 1000 ° C. for 1 hour in an air atmosphere to obtain 0.7 g of hollow particles of Synthesis Example 1. ..

[Synthesis Example 2]
Titanium oxide-silica hollow structure particles were obtained in the same manner as in Synthesis Example 1 except that the titanium tetrabutoxide used in Synthesis Example 1 was changed to 7 g and tetraethyl orthosilicate was changed to 0.6 g (anathase type).

The physical characteristics of the particles obtained in Synthesis Examples 1 and 2 are shown in Table 1 below.

[Example 1]
2.5 g of hollow structure particles prepared in Synthesis Example 1, 7 g of dipentaerythritol poly (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), 1-hydroxycyclohexylphenyl ketone (manufactured by BASF) as a photoreaction initiator. Irgacure 184) 0.5 g, DISPERBYK-168 (manufactured by Big Chemie Japan Co., Ltd.) 0.2 g as a dispersant, and 10 g of propylene glycol monomethyl ether acetate as a solvent are mixed, and a disperser (manufactured by Primix Corporation, Philmix) is used. The dispersion liquid 1 was prepared.

After allowing the dispersed dispersion to stand for 1 day, it was applied onto a glass substrate using a spin coater so that the film thickness after heat treatment was 10 μm, and dried at 100 ° C. for 2 minutes using a hot plate. .. Next, the cured film 1 of the present invention was produced by UV irradiation.

[Example 2]
The dispersion liquid 2 and the cured film 2 were prepared in the same manner as in Example 1 except that the hollow structure particles used in Example 1 were changed to the hollow structure particles of Synthesis Example 2.

[Comparative Example 1]
As a comparative example, the dispersion liquid 3 and the cured film 3 were prepared in the same manner as in Example 1 except that the hollow structure particles 1 used in Example 1 were changed to titanium oxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., CR-50). ..

[Dispersion stability]
After allowing the prepared dispersion to stand for one day, the sedimentation property and redispersibility in the dispersion, and the appearance of the cured film were evaluated by the following methods.

Precipitability 〇: The entire dispersion liquid exhibits a uniform white color.
Δ: The upper layer of the dispersion liquid is partially separated in a gradation pattern.
X: The upper layer of the dispersion is completely separated.

Redispersible <br/> ○: redispersed shaking several times vessel containing dispersion.
Δ: When the container containing the dispersion liquid is shaken several times, a part of the container remains at the bottom.
X: Even if the container containing the dispersion liquid is shaken several times, it remains on the entire bottom surface.

[Appearance of cured film]
〇: Titanium oxide is uniformly dispersed in the film, and the appearance of the film is uniform.
X: The concentration of titanium oxide is uneven in the film, and the appearance of the film is not uniform.

As is clear from Table 2, the resin composition of the present invention has high sedimentation stability, so that a uniform cured film can be produced.

According to the inventions described in 12) to 21) above, it is excellent in sedimentation stability and particle strength, for example, when it is used as a powder cosmetic, it is excellent in brilliance and glossiness, and when it is contained as a colorant. It is possible to provide rutile-type titanium oxide hollow particles capable of obtaining a white ink having good hiding power. This can solve the following problems.
That is, hollow particles containing silica or metal oxide are expected to be applied as white pigments and the like. However, as confirmed by the present inventors, it was found that the conventional hollow particles have room for improvement in sedimentation stability and particle strength.
When a white ink is prepared by using hollow particles having poor sedimentation stability, for example, as a white pigment, the dispersed state is easily broken and the pigment is likely to be in a sedimented state. Therefore, before using the white ink, it is necessary to return the precipitated pigment to a uniformly dispersed state by an operation such as stirring, which is poor in operability.
Further, if the particle strength of the hollow particles is low, the hollow particles are broken when the dispersion liquid is prepared, and the hollow state cannot be maintained. Therefore, it is difficult to obtain good dispersion stability due to the hollow particles. Further, if the hollow particles are broken during the preparation of the dispersion, particles of various sizes are generated in the dispersion, which makes it difficult to prepare a dispersion having a small particle size distribution and a uniform primary particle size. .. As a result, it becomes difficult to obtain a white ink having good hiding power.
Therefore, it is an object of the inventions described in 10) to 20) to provide hollow particles having excellent sedimentation stability and particle strength and good hiding properties, a dispersion liquid containing the hollow particles, and its use.

The white ink described in 21) and cosmetics as examples of other uses are described below.
<White ink>
White ink can be produced by using the above dispersion liquid. The white ink will be described below.
The white ink according to the present embodiment contains the above-mentioned hollow particles according to the present embodiment as a colorant. The white ink according to the present embodiment can be used as an ink selected from the group consisting of water-based ink, latex ink, solvent ink, and ultraviolet curable ink. Such various inks can be prepared by appropriately adding necessary components to each ink together with hollow particles as a colorant.
The rutile-type titanium oxide hollow particles used for white ink have an A / B value of 0.1 or more and less than 0.3 when the hollow diameter of the hollow particles is A and the particle diameter of the hollow particles is B. The case is preferable. That is, 70% or more of the particle size is a rutile-type titanium oxide shell, and the structure has a hollow inside. The preferable upper limit of the A / B value is 0.29, more preferably 0.28, and particularly preferably 0.25. The preferable lower limit is 0.12, more preferably 0.14, and particularly preferably 0.16. Therefore, 0.16 or more and 0.25 or less is the most preferable range.

[Latex ink]
When the white ink according to the present embodiment is a latex ink, the white ink preferably contains water, a water-soluble organic solvent, and a resin. The resin in the white ink can also be in an emulsified or suspended state.
Examples of the water and the water-soluble organic solvent include those contained in the water-based ink.

Examples of the resin include water-soluble vinyl-based resins, acrylic-based resins, alkyd-based resins, polyester-based resins, phenoxy-based resins, polyolefin-based resins, and other modified resins. Among these, acrylic resins, water-soluble polyurethane resins, water-soluble polyester resins, water-soluble acrylic resins and the like are preferable.

[Solvent ink]
When the white ink according to the present embodiment is a solvent ink, the white ink preferably contains a dispersant and a non-aqueous organic solvent.

Examples of the dispersant include a solvene series manufactured by Nisshin Kagaku Kogyo Co., Ltd .; a Floren series manufactured by Kyoeisha Chemical Co., Ltd .; an ANTI-TERRA series manufactured by Big Chemie Japan Co., Ltd., a DISPERBYK series; and the like.

Examples of the non-aqueous organic solvent include hydrocarbon-based, ester-based, and ketone-based solvents. Examples of the hydrocarbon solvent include n-hexane, n-heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene and the like. Examples of the ester solvent include propyl formate, -n-butyl formate, isobutyl formate, amyl formate, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n-butyl acetate, isobutyl acetate, second butyl acetate and -n acetate. -Amil, isoamyl acetate, methyl isoamyl acetate, second hexyl acetate, methyl propionate, ethyl propionate, -n-butyl propionate, butyl butylate, ethyl butyrate, methyl lactate, γ-butyrolactone and the like can be mentioned. Examples of the ketone solvent include methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, mesityl ketone and the like.

[UV curable ink]
When the white ink according to the present embodiment is an ultraviolet curable ink, the white ink preferably contains a curable monomer or a curable oligomer, and a photocuring initiator. Further, the white ink may further contain a photocuring sensitizer.

As used herein, the term "curable monomer" means a monomer that polymerizes by applying an external stimulus to form a cured product. Further, the "curable oligomer" means an oligomer that polymerizes by applying an external stimulus to form a cured resin.
Examples of the curable monomer include radical polymerization type low-viscosity acrylic monomers; cationic polymerization type vinyl ethers, oxetane-based monomers, cyclic aliphatic epoxy monomers, and the like.
Examples of the curable oligomer include cationic polymerization type acrylic oligomers.

Examples of the low-viscosity acrylic monomer include methoxypolyethylene glycol acrylate, phenoxyethylene glycol acrylate, phenoxydiethylene glycol acrylate, phenoxyhexaethylene glycol acrylate, methoxypolyethylene glycol methacrylate, 3-chloro-2-hydroxypropyl methacrylate, β-carboxyethyl acrylate, and acryloyl. Morforin, diacetone acrylic amide, vinylformamide, N-virylpyrrolidone, neopentyl glycol dimethacrylate 2PO neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, Glycerin dimethacrylate, glycerin acrylate methacrylate, modified epoxidized polyethylene glycol diacrylate, -2- (2-vinyloxyethoxy) ethyl acrylate, ethoxylated trimethyl propantriacrylate, ethoxylated glycerin triacrylate, EO-modified trimethyl propanthry Examples include acrylate.

Examples of vinyl ethers include hydroxybutyl vinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, propylene carbonate propenyl ether, dodecyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanevinyl ether, diethylene glycol divinyl ether, 2-ethylhexyl vinyl ether, and dipropylene. Glycol divinyl ether, tripropylene glycol divinyl ether, hexanediol divinyl ether, octadecyl vinyl ether, butanediol divinyl ether, isopropyl vinyl ether, allyl vinyl ether, 1,4-butanediol divinyl ether, nonadiol divinyl ether, cyclohexanediol vinyl ether, cyclohexanedimethanol Vinyl ether, triethylene glycol divinyl ether, trimethylpropan trivinyl ether, pentaerythritol tetravinyl ether, VEEA -2- (2-vinyloxyethoxy) ethyl acrylate, VEEM -2-vinyloxyethoxy) ethyl, etc. Can be mentioned.

Examples of oxetane-based monomers include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [((3-ethyloxetane-3-yl) methoxy) methyl] benzene, and 3-ethyl-3-[((3-ethyloxetane-3-yl) methoxy) methyl] benzene. Ethyloxetane-3-yl) methoxy) methyl] oxetane, 3-ethyl-3- (phenoxymethyl) oxetane and the like can be mentioned.

As the cyclic aliphatic epoxy monomer, Celloxide 2000, Celloxide 3000 (manufactured by Daicel Co., Ltd.); CYRACURE UVR-6015, CYRACURE UVR-6028, CYRACURE UVR-6105, CYRACURE UVR-6128, CYRACURE ERR-4 Dow Chemical Co., Ltd.); DCPD-EP and its derivatives (manufactured by Maruzen Petrochemical Co., Ltd.); and the like.

Examples of the acrylic oligomer include hyperbranched polyester acrylate, polyester acrylate, urethane acrylate, and epoxy acrylate.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used depending on the intended purpose. Specific examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 1-hydroxycyclohexylphenylketone (Irgacure 184; manufactured by BASF), 2-hydroxy-2-methyl- [4- (1-Methylvinyl) phenyl] propanol oligomer (Esacure ONE; manufactured by Lamberti), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one ( Irga Cure 2959; manufactured by BASF), 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irga) Cure 127; BASF), 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651; BASF), 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (DaroCure 1173; BASF) 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one (Irgacure 907; manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4) -Molholinophenyl) -butane-1-one, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone and the like.

Among these, from the viewpoint of curability and transparency, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propane-1-one is preferred.

Further, the photopolymerization initiator may be an intramolecular hydrogen abstraction type photopolymerization initiator. Intramolecular hydrogen abstraction type photopolymerization initiators include oxyphenyl acetic acid methyl ester (Irgacure MBF; manufactured by BASF), oxyphenyl acetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxy. Examples thereof include an oxyphenyl-based photopolymerization initiator such as a mixture of phenylacetic acid and 2- (2-hydroxy-ethoxy) ethyl ester (Irgacure 754; manufactured by BASF).

A photopolymerization initiator such as amines can also be used in combination with the photopolymerization initiator. Examples of amines include benzoic acid 2-dimethylaminoethyl ester, dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester and the like.

[Preparation method, etc.]
The white ink according to the present embodiment can be prepared by adding hollow particles to a target liquid medium such as water or a water-insoluble water-soluble solvent and dispersing them by a known method. Examples of the dispersion method include a method in which a colorant and a dispersant are placed in a high-speed stirring homogenizer, a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like to perform dispersion. .. As an example, when a sand mill is used, beads having a particle size of about 0.01 mm to 1 mm can be used, and the filling rate of the beads can be appropriately set to perform the dispersion treatment.

The dispersion liquid thus obtained may be subjected to operations such as filtration and centrifugation. By this operation, the size of the particle size of the particles contained in the dispersion liquid can be made uniform.

All of the above-mentioned components may be used alone or in combination of two or more.
Further, with respect to all the above-mentioned matters, the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable. The same applies to a combination of a preferable one and a more preferable one, a combination of a more preferable one and a more preferable one, and the like.

<Cosmetics>
Cosmetics can be produced using the rutile-type hollow titanium oxide particles of the present invention. The cosmetics will be described below.
For the rutyl-type hollow titanium oxide particles, for example, esters, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, coating agents, UV absorbers, metal ion blockers, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, high molecular weight emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. Can be appropriately blended as needed and produced by a conventional method according to the desired dosage form.
The cosmetics using the rutile-type titanium oxide hollow particles of the present invention can be used for various purposes for controlling the color of skin and lips and / or coloring and / or shielding ultraviolet rays. The cosmetic may be a solid cosmetic, a liquid cosmetic, or a powder cosmetic.
Liquid cosmetics include, for example, lotions, emulsions, gels, creams, beauty liquids, sunscreen cosmetics, packs, masks, hand creams, body lotions, and basic cosmetics such as body creams; and facial cleansers. Examples include cleansing (makeup remover), body shampoo, shampoo, rinse, and cleaning cosmetics such as treatments. Further, for example, a so-called cleansing lotion that also serves as a lotion and cleansing, a cleansing milk, a cleansing cream, or the like may be used as a cosmetic composition that also has the functions of a basic cosmetic and a cleaning cosmetic. Furthermore, the cosmetic composition of the present invention may be a rinse-off type or a leave-on type.
As the solid cosmetics, for example, loose powder type cosmetics; solid powder cosmetics formed by compression molding or removing the solvent after filling in a container; pouring a paste into a container. Kneaded cosmetics formed by; stick-type cosmetics; and the like. Specific examples include foundation, stick foundation, face powder, lipstick, blusher, eye color, eyebrow, makeup base, daytime beauty essence, sunscreen, concealer, bronzer, lip color, BB cream and the like.
As the product form of the powder cosmetics, any product form in the category of the powder cosmetics can be taken. Specifically, it can take product forms such as foundation, eye shadow, cheek color, body powder, perfume powder, baby powder, pressed powder, deodorant powder, and face powder.

Hereinafter, embodiments of the invention of 11) will be described below as reference examples.

[Reference Synthesis Example 1: Preparation of Ethanol Dispersion Solution (Dispersion Solution 1) of Template Particles]
13.5 g of styrene, 2.4 g of methacrylic acid, and 0.05 g of potassium persulfate are added to 600 g of distilled water, emulsion polymerization is performed at 80 ° C., and an aqueous dispersion containing styrene-methacrylic acid polymer particles (template particles) is prepared. Obtained. The primary particle size of the obtained template particles was 158 nm. The dispersion liquid 1 was prepared by adding ethanol while concentrating the aqueous dispersion liquid of the template particles with an evaporator and replacing the water with ethanol. The content of the template particles in the dispersion liquid 1 was 9% by mass.

[Reference Example 1]
(Step 1: Step of obtaining first core / shell particles)
23.5 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 1 (1.5 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 50 g of titanium tetrabutoxide and 15 g of 2% aqueous ammonia were added in 10 portions every 0.5 hours and reacted at 10 ° C. for 4 hours to obtain a solution containing the first core / shell particles. Obtained. The obtained solution was used in the next step 2 without isolation and purification.

(Step 2: Step of obtaining second core / shell particles)
To the solution obtained in step 1, 1 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 solution. The obtained liquid was centrifuged at 15000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60 ° C. to obtain 30 g of the target second core / shell particles. ..

(Step 3: Step of manufacturing hollow structure particles)
30 g of the second core / shell particles obtained in step 2 was placed on a ceramic board, set in a firing furnace, and fired at 800 ° C. for 1 hour in a hydrogen atmosphere. After replacing the hydrogen atmosphere with an air atmosphere, the particles were calcined at 1000 ° C. for another 1 hour to obtain 16 g of hollow structure particles of Example 1 containing titanium oxide and silica.

[Reference Example 2]
30 g of hollow structure particles of Example 2 containing titanium oxide and silica were obtained in the same manner as in Example 1 except that 1 g of tetraethyl orthosilicate used in Step 2 of Example 1 was changed to 5 g.

[Reference Example 3]
30 g of hollow structure particles of Example 3 containing titanium oxide and silica were obtained in the same manner as in Example 1 except that the dispersion liquid 1 (1.5 g) used in step 1 of Example 1 was changed to 2.5 g. Obtained.

[Reference Synthesis Example 2: Preparation of Ethanol Dispersion Solution (Dispersion Solution 2) of Template Particles]
10 g of styrene, 1.4 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 90 ° C. to obtain an aqueous dispersion containing styrene-methacrylic acid polymer particles (template particles). .. The primary particle size of the obtained template particles was 112 nm. The dispersion liquid 2 was prepared by adding ethanol while concentrating the aqueous dispersion liquid of the template particles with an evaporator and replacing the water with ethanol. The content of the template particles in the dispersion liquid 2 was 6% by mass.

[Reference Example 4]
(Step 1: Step of obtaining first core / shell particles)
23.5 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 2 (1 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 50 g of titanium tetrabutoxide and 15 g of 2% aqueous ammonia were added in 10 portions every 0.5 hours and reacted at 10 ° C. for 4 hours to obtain a solution containing the first core / shell particles. Obtained. The obtained solution was used in the next step 2 without isolation and purification.

(Step 2: Step of obtaining second core / shell particles)
To the solution obtained in step 1, 1 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 solution. The obtained liquid was centrifuged at 15000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60 ° C. to obtain 30 g of the target second core / shell particles. ..

(Step 3: Step of manufacturing hollow structure particles)
30 g of the second core / shell particles obtained in step 2 was placed on a ceramic board, set in a firing furnace, and fired at 800 ° C. for 1 hour in a hydrogen atmosphere. After replacing the hydrogen atmosphere with an air atmosphere, the particles were calcined at 1000 ° C. for another 1 hour to obtain 16 g of hollow structure particles of Example 4 containing titanium oxide and silica.

[Reference Comparative Example 1]
[Synthesis Example 3: Preparation of Ethanol Dispersion Solution (Dispersion Solution 3) of Template Particles]
The dispersion liquid 3 was prepared in the same manner as in Synthesis Example 1 except that 13.5 g of styrene used in Synthesis Example 1 was changed to 21 g. The primary particle size of the obtained template particles was 237 nm. The content of the template particles in the dispersion liquid 3 was 9% by mass.

(Step 1: Step of obtaining first core / shell particles)
20 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 3 (5 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 3 g of titanium tetrabutoxide and 3 g of 2% aqueous ammonia were added in 3 portions every 0.5 hours and reacted at 10 ° C. for 4 hours to obtain a solution containing the first core / shell particles. Obtained. The obtained solution 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, 0.1 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 obtained liquid was centrifuged at 15000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60 ° C. to obtain 2.0 g of the target second core / shell particles. Obtained.

(Step 3: Step of manufacturing hollow structure particles)
2.0 g of the second core / shell particles obtained in step 2 was placed on a ceramic board and set in a firing furnace, fired at 800 ° C. for 1 hour in a hydrogen atmosphere, and subsequently 1 at 800 ° C. in an air atmosphere. By firing for a time, 0.9 g of hollow structure particles of Comparative Example 1 containing titanium oxide and silica were obtained.

[Reference Comparative Example 2]
[Reference Synthesis Example 3: Preparation of Ethanol Dispersion Solution (Dispersion Solution 3) of Template Particles]
25 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 size of the obtained template particles was 280 nm. The dispersion liquid 3 was prepared by adding ethanol while concentrating the aqueous dispersion liquid of the template particles with an evaporator and replacing the water with ethanol. The content of the template particles in the dispersion liquid 1 was 9% by mass.

(Step 1: Step of obtaining first core / shell particles)
23.5 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 3 (1.5 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 50 g of titanium tetrabutoxide and 15 g of 2% aqueous ammonia were added in 10 portions every 0.5 hours and reacted at 10 ° C. for 4 hours to obtain a solution containing the first core / shell particles. Obtained. The obtained solution was used in the next step 2 without isolation and purification.

(Step 2: Step of obtaining second core / shell particles)
To the solution obtained in step 1, 5 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 solution. The obtained liquid was centrifuged at 15000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60 ° C. to obtain 30 g of the target second core / shell particles. ..

(Step 3: Step of manufacturing hollow structure particles)
30 g of the second core / shell particles obtained in step 2 was placed on a ceramic board, set in a firing furnace, and fired at 800 ° C. for 1 hour in a hydrogen atmosphere. After replacing the hydrogen atmosphere with an air atmosphere, the particles were calcined at 1000 ° C. for another 1 hour to obtain 16 g of hollow structure particles of Example 1 containing titanium oxide and silica.

[Reference Comparative Example 3]
(Step 1: Step of obtaining first core / shell particles)
23.5 g of ethanol, 8 g of acetonitrile, 0.1 g of polyvinylpyrrolidone, and dispersion liquid 2 (0.5 g) were cooled to 10 ° C. to obtain a liquid. To this solution, 70 g of titanium tetrabutoxide and 14 g of 2% aqueous ammonia were added in 35 portions every 0.5 hours and reacted at 10 ° C. for 4 hours to obtain a solution containing the first core / shell particles. Obtained. The obtained solution was used in the next step 2 without isolation and purification.

(Step 2: Step of obtaining second core / shell particles)
To the solution obtained in step 1, 10 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 solution. The obtained liquid was centrifuged at 15000 rpm for 25 minutes to remove the supernatant, and the residue was dried in a vacuum dryer heated to 60 ° C. to obtain 44 g of the target second core / shell particles. ..

(Step 3: Step of manufacturing hollow structure particles)
30 g of the second core / shell particles obtained in step 2 was placed on a ceramic board, set in a firing furnace, and fired at 800 ° C. for 1 hour in a hydrogen atmosphere. After replacing the hydrogen atmosphere with an air atmosphere, the mixture was calcined at 1000 ° C. for another 1 hour to obtain 26 g of hollow structure particles of Example 4 containing titanium oxide and silica.

Silica content (mol%) in the hollow structure particles obtained in each of the above-mentioned Examples and Comparative Examples, the primary particle diameter B (nm) of the hollow structure particles, the inner diameter A (nm) of the hollow structure, and the ratio thereof. a / B, the content of the rutile type titanium oxide F _{R (%} by weight) and a sphericity shown in table 1 below.

As shown in Table 3, when A / B was lower than 0.1, the hollow structure could not be maintained and the hollow structure particles could not be produced.

[Strength test of hollow structure particles]
0.007 g of each hollow structure particle produced in Reference Examples 2 and 3 and Comparative Example 1 was added to 10 mL of distilled water, and ultrasonically treated in an ultrasonic bath (manufactured by Honda Electronics Corporation, W-113MkII) for 10 minutes. To obtain a liquid (before the strength test). The obtained liquid and 6 g of zirconia beads having a diameter of 0.03 mm were added to Philmix (RM, manufactured by Primix Corporation) and operated at a rotation speed of 4000 rpm for 10 minutes to obtain a liquid (after the strength test).

Distilled water was added to each of the liquids obtained before and after the strength test to dilute them 10-fold, and the turbidity was measured. The turbidity was displayed as a TURB value. The TURB value is the concentration for the kaolin standard solution. The rate of change of the TURB value was calculated according to the following formula, and the strength of the hollow structure particles was determined. The strength test results are shown in Table 2 below. The rate of change of the TURB value is shown in Table 4 below, rounded off to the first decimal place.
Rate of change of TURB value (%) = (TURB value after intensity test (mg / L) / TURB value before intensity test (mg / L)) × 100

[Test for the presence or absence of pores]
In order to confirm whether or not there are pores leading to internal pores on the surface of the hollow structure particles, a pore distribution measuring device (Microtrac Bell Co., Ltd., BELSORP-miniII) is used for relative pressure. The amount of adsorption and the amount of desorption were measured, and if pores were present, they were analyzed by the BJH (Barrett-Joyner-Halenda) method to determine the pore area.

As is clear from the results of the rate of change of the TURB value in Table 4, the hollow structure particles having an A / B of less than 0.3 have a higher value than the hollow structure particles having an A / B of more than 0.3. Was there. This is because the hollow structure particles of Reference Examples 2 and 3 maintain a hollow structure more than the hollow structure particles of Reference Comparative Example 1.
Further, the hollow structure particles having an A / B of more than 0.3 have pores leading to the internal pores, and when dispersed in the liquid, the solvent penetrates into the hollow structure particles to cause sedimentation. Improvement is hindered.
By using the hollow structure particles of the present invention, the hollow structure collapse during dispersion mixing is prevented when the dispersion liquid, the white ink and the cosmetic are prepared, so that the original functions of the hollow structure particles can be exhibited.

The resin composition of the present invention can provide a resin composition having excellent sedimentation stability while maintaining conventional functions such as light scattering property as compared with a conventional resin composition containing titanium oxide fine particles.

Claims (11)

(A) A resin composition containing rutile-type titanium oxide hollow particles. The resin composition according to claim 1, further containing (B) a curable compound and (C) a curing agent. The resin composition according to claim 1 or 2, further containing (D) a solvent. The resin composition according to any one of claims 1 to 3, wherein the (A) rutile-type titanium oxide hollow particles are hollow particles having rutile-type titanium oxide and silica. The resin composition according to any one of claims 1 to 4, wherein the primary average particle diameter of the (A) rutile-type titanium oxide hollow particles is 0.1 to 1.0 μm. The resin composition according to any one of claims 1 to 5, wherein the ratio of the hollow diameter A / particle diameter B of the (A) rutile-type titanium oxide hollow particles is 0.3 to 0.95. thing. The resin composition according to any one of claims 1 to 6, wherein the rutile-type titanium oxide hollow particles have a spherical shape. The invention according to any one of claims 1 to 7, wherein the (B) curable compound is at least one compound selected from (B-1) thermosetting resin and (B-2) photocurable resin. Resin composition. The resin according to any one of claims 1 to 8, wherein the (C) curing agent is at least one curing agent selected from (C-1) thermosetting agent and (C-2) radical polymerization initiator. Composition. A cured film obtained by curing the resin composition according to any one of claims 1 to 9. A display device having the cured film according to claim 11.