Colored resin particle and dimmer laminate

Abstract

To provide colored resin particles which highly accurately control a gap between base materials, and can suppress light omission.SOLUTION: Colored resin particles contain resin particles and a colorant, wherein as for each of the colored resin particles before light irradiation and the colored resin particles after the light irradiation irradiated with light at an integrated light quantity of 540 MJ / m2, when brightness in an L*a*b* color system according to JIS Z8781-4:2013 is measured, brightness L0* of the colored resin particles before the light irradiation is 0 or more and 60 or less, and a ratio of the brightness L0* of the colored resin particles before the light irradiation to brightness L540* of the colored resin particles after the light irradiation is 0.3 or more.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to colored resin particles and a light-controlling laminate using the colored resin particles. [Background technology]

[0002] Light-control materials such as light-control glass and light-control films have the property that their light transmittance changes depending on whether or not an electric field is applied, making it possible to adjust the amount of incident light. Depending on the mechanism by which they change the light transmittance, light-control materials are broadly classified into SPD (Suspended Particle Device) type and PDLC (Polymer Dispersed Liquid Crystal) type.

[0003] The SPD method is a method in which a light control suspension is dispersed in a resin matrix. The light control suspension contains light control particles. The light control particles are responsive to an electric field. In the SPD method, when no electric field is applied, the light control particles dispersed in the light control suspension absorb, scatter, or reflect light due to Brownian motion, so that the incident light does not pass through the light-adjusting material. When an electric field is applied, the light control particles are polarized and align in a direction parallel to the electric field, so that the incident light passes through the light-adjusting material. In this way, the SPD method can adjust the light transmittance by utilizing the polarization orientation of the light control particles.

[0004] The PDLC method is a method in which liquid crystal is dispersed in a resin matrix. The PDLC method can be embodied in a form in which liquid crystal and a resin matrix are dispersed as a continuous phase, or in a form in which liquid crystal is dispersed as liquid crystal capsules in a resin matrix. When no electric field is applied, the liquid crystal molecular orientation is not uniform, and the difference in refractive index between the resin matrix and the liquid crystal causes the incident light to be scattered in the light-adjusting material, resulting in an opaque state. When an electric field is applied, the liquid crystal molecules are aligned in a direction parallel to the electric field. At this time, the refractive index of the resin matrix and the refractive index of the liquid crystal become equivalent, allowing the incident light to pass through the light-adjusting material, resulting in a transparent state. In this way, the PDLC method adjusts the light transmittance by utilizing the molecular orientation of the liquid crystal.

[0005] When a light-controlling laminate is produced using a light-controlling material, a spacer may be used to control the gap between two substrates. Examples of the spacer include resin particles. As an example of such resin particles, the following Patent Document 1 discloses fine particles (resin particles) in which particles containing a crosslinkable polymer material are coated with a fluorine-based resin or a silicon-based resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-010540 Summary of the Invention [Problem to be solved by the invention]

[0007] When conventional resin particles such as those described in Patent Document 1 are used as spacers, light leakage, in which light passes through the resin particles, may occur. This light leakage phenomenon poses the problem of causing degradation of display quality, such as reduced contrast and white spots.

[0008] An object of the present invention is to provide colored resin particles capable of controlling the gap between substrates with high precision and suppressing light leakage. Another object of the present invention is to provide a light-controlling laminate capable of controlling the gap between substrates with high precision and suppressing light leakage. [Means for solving the problem]

[0009] According to a broad aspect of the present invention, a coating composition is provided that includes resin particles and a colorant, and the coating composition includes colored resin particles and a coloring agent before light irradiation at 540 MJ / m 2 When the lightness in the L*a*b* color system in accordance with JIS Z8781-4:2013 is measured for each of the colored resin particles after light irradiation with an integrated light amount of 10 ... 540 The colored resin particles are provided in which the ratio of * to is 0.3 or more.

[0010] In a specific aspect of the colored resin particles according to the present invention, the 20% K value is 100 N / mm 2 More than 5000N / mm 2 The following is the result.

[0011] In a specific aspect of the colored resin particles according to the present invention, the volume resistivity is 1.0×10 9 Ω·cm or more.

[0012] In a specific aspect of the colored resin particles according to the present invention, the average particle size is 1 μm or more and 150 μm or less.

[0013] In a specific aspect of the colored resin particles according to the present invention, the particles do not contain particles having a particle diameter of 1.2 times or more the average particle diameter, or contain particles having a particle diameter of 1.2 times or more the average particle diameter in an amount of 1000 ppm or less.

[0014] In a specific aspect of the colored resin particles according to the present invention, the CV value of the particle size is 10% or less.

[0015] In a specific aspect of the colored resin particles according to the present invention, the colorant includes an organic black pigment, titanium black particles, or carbon black particles.

[0016] In a specific aspect of the colored resin particles according to the present invention, the colored resin particles contain the colorant in an amount of 20% by weight or less relative to 100% by weight of the colored resin particles.

[0017] In a specific aspect of the colored resin particles according to the present invention, the specific gravity is 1.5 or less.

[0018] In a specific aspect of the colored resin particles according to the present invention, the colored resin particles contain a component derived from a polyfunctional (meth)acrylate compound.

[0019] In a specific aspect of the colored resin particles according to the present invention, the colored resin particles contain a component derived from a polyfunctional (meth)acrylate compound in an amount of 50% by weight or more relative to 100% by weight of the colored resin particles.

[0020] In a specific aspect of the colored resin particles according to the present invention, the colored resin particles are used as spacers.

[0021] In a specific aspect of the colored resin particles according to the present invention, the colored resin particles are used as spacers in a light-adjusting laminate.

[0022] According to a broad aspect of the present invention, there is provided a photochromic laminate comprising a first substrate, a second substrate, and a photochromic layer disposed between the first substrate and the second substrate, the photochromic layer including the colored resin particles described above. Effect of the Invention

[0023] The colored resin particles according to the present invention contain resin particles and a colorant. 2When the lightness in the L*a*b* color system in accordance with JIS Z8781-4:2013 is measured for each of the colored resin particles after light irradiation with an integrated light amount of 10 ... 540 The ratio of * to is 0.3 or more. Since the colored resin particles according to the present invention have the above-mentioned configuration, it is possible to control the gap between the base materials with high precision and suppress light leakage. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 is a cross-sectional view that illustrates a colored resin particle according to a first embodiment of the present invention. [Diagram 2] FIG. 2 is a cross-sectional view that illustrates a PDLC-type light control laminate that includes colored resin particles according to the first embodiment of the present invention. [Diagram 3] FIG. 3 is a cross-sectional view that illustrates a schematic diagram of an SPD type light control laminate that includes colored resin particles according to a first embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The present invention will be described in detail below. In this specification, for example, "(meth)acrylate" means one or both of "acrylate" and "methacrylate", and "(meth)acrylic" means one or both of "acrylic" and "methacrylic".

[0026] (Colored resin particles) The colored resin particles according to the present invention contain resin particles and a colorant. 2When the lightness in the L*a*b* color system in accordance with JIS Z8781-4:2013 is measured for each of the colored resin particles after light irradiation with an integrated light amount of 10 ... 540 The ratio to * is 0.3 or more.

[0027] Since the colored resin particles according to the present invention have the above-mentioned configuration, the gap between the substrates can be controlled with high precision and light leakage can be suppressed.

[0028] In addition, conventional colored particles that are colored with dyes may fade due to exposure to light for a long period of time, resulting in a decrease in light blocking properties and causing light leakage. On the other hand, the colored resin particles according to the present invention have the above-mentioned configuration, and therefore can suppress light leakage for a long period of time even when exposed to light for a long period of time.

[0029] From the viewpoint of more effectively suppressing light leakage, in the above measurement, the lightness L0* of the colored resin particles before light irradiation is preferably 1 or more, more preferably 3 or more, and is preferably 55 or less, more preferably 40 or less, and even more preferably 30 or less.

[0030] From the viewpoint of more effectively suppressing the light leakage, in the above measurement, the lightness L 540 * is preferably 1 or more, more preferably 3 or more, even more preferably 4 or more, and is preferably 60 or less, more preferably 50 or less, even more preferably 40 or less.

[0031] From the viewpoint of more effectively suppressing light leakage, in the above measurement, the lightness L0* of the colored resin particles before light irradiation is smaller than the lightness L 540 *Ratio to (L0* / L 540The ratio (L0* / L*) is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more, and particularly preferably 0.8 or more. 540 *) is not particularly limited. 540 *) may be less than or equal to 1.0.

[0032] The lightness L0* of the colored resin particles before light irradiation and the lightness L of the colored resin particles after light irradiation 540 * can be measured as follows. A plate-shaped sample having the same composition as the colored resin particles is prepared. The plate-shaped sample is irradiated with 255 W / m 2 588 hours at illuminance of 540MJ / m 2 The light was measured at 10 arbitrary points on the sample before and after the light irradiation using a color difference meter with a measurement range of a circle with a diameter of 8 mm, and the average lightness L0* and lightness L 540 * The color difference meter may be the "TES-3250" manufactured by SATOTECH.

[0033] In addition, the lightness L0* of the colored resin particles before light irradiation and the lightness L 540 The colored resin particles before and after light irradiation are supported on an adhesive tape, and the lightness is measured at any 10 points of the colored resin particles using a colorimeter with a measurement range of a circle with a diameter of 8 mm, and the average values ​​are designated as lightness L0* and lightness L 540 * The color difference meter may be a "TES-3250" manufactured by SATOTECH Co., Ltd. After the light irradiation, the colored resin particles are irradiated with light at 255 W / m using a Sunshine carbon arc lamp. 2 588 hours at illuminance of 540MJ / m 2 The colored resin particles after the light irradiation are irradiated with light at 180 W / m using a super xenon lamp. 2 830 hours at illuminance of 540MJ / m 2The colored resin particles after the light irradiation may be obtained by irradiating the colored resin particles with light at a power of 60 W / m using a xenon lamp. 2 2500 hours at illuminance of 540MJ / m 2 ) may be obtained by irradiating the colored resin particles with light.

[0034] The lightness L0* of the colored resin particles before light irradiation and the lightness L of the colored resin particles after light irradiation 540 As a method for easily controlling * within a suitable range, a method for adjusting the type and content of the colorant may be mentioned.

[0035] From the viewpoint of more effectively suppressing light leakage, the visible light transmittance of the colored resin particles is preferably 40% or less, more preferably 20% or less, and even more preferably 10% or less.

[0036] The visible light transmittance of the colored resin particles can be measured as follows: A plate-shaped sample having the same composition as the colored resin particles is prepared, and spectroscopic measurement or the like is carried out to measure the visible light transmittance in accordance with ISO13837:2008. It can also be measured by a method in accordance with JIS K6714.

[0037] The volume resistivity of the colored resin particles is preferably 1.0×10 9 Ω cm or more, preferably 1.0×10 10 Ω cm or more, more preferably 1.0×10 11 Ω cm or more, particularly preferably 1.0×10 12 When the volume resistivity of the colored resin particles is equal to or higher than the lower limit, the insulation reliability of the colored resin particles can be improved, and as a result, the conduction reliability of the obtained light-controlling laminate can be improved. The upper limit of the volume resistivity of the colored resin particles is not particularly limited. The volume resistivity of the colored resin particles is 1.0×10 20 It may be less than Ω cm, and may be 1.0×10 18 It may be Ω·cm or less.

[0038] The volume resistivity of the colored resin particles can be measured as follows. Using a powder resistivity measurement system (for example, Mitsubishi Chemical Analytech's "Powder Resistivity Measurement System MCP-PD51"), loads from 0 kN to 20 kN in 4 kN increments are applied to the colored resin particles filled in a probe using a hydraulic pump. The volume resistivity of the colored resin particles is measured with each load (0 kN, 4 kN, 8 kN, 12 kN, 16 kN, and 20 kN) applied, and the lowest value is taken as the volume resistivity of the colored resin particles.

[0039] The 20% K value of the colored resin particles is preferably 100 N / mm 2 More preferably, 700N / mm 2 More preferably, 1000N / mm 2 or more, preferably 5000N / mm 2 Less than or equal to 4000N / mm 2 Less than 3000N / mm 2 or less. When the 20% K value of the colored resin particles is equal to or greater than the lower limit and equal to or less than the upper limit, the gap between the substrates can be controlled with even higher precision, and damage to the substrates can be prevented. When the 20% K value of the colored resin particles is equal to or greater than the lower limit and equal to or less than the upper limit, damage to the colored resin particles can be suppressed, so that outflow of the colorant in the colored resin particles can be suppressed, and the occurrence of short circuits can be suppressed. As a result, the electrical conductivity reliability of the obtained light-controlling laminate can be improved.

[0040] The 20% K value of the colored resin particles can be measured as follows. Using a microcompression tester, the colored resin particles are compressed with a smooth cylindrical indenter end face (diameter 50 μm, made of diamond) under conditions of 25° C. and a maximum test load of 20 mN for 60 seconds. The load value (N) and compression displacement (mm) at this time are measured. From the obtained measured values, the 20% K value can be calculated by the following formula. As the microcompression tester, for example, Fischer Scope H-100 manufactured by Fischer Co., Ltd. can be used.

[0041] 20% K value (N / mm 2)=(3 / 2 1 / 2 )·F·S -3 / 2 ·R -1 / 2 F: Load value (N) when colored resin particles are compressed and deformed by 20% S: Compressive displacement (mm) when the colored resin particles are compressed by 20% R: Radius of colored resin particle (mm)

[0042] Methods for easily controlling the 20% K value of the colored resin particles within a suitable range include adjusting the number of polymerizable functional groups and molecular weight of the material (polymerizable monomer) for forming the resin particles, or adjusting the type and content of the colorant, thereby adjusting the crosslink density of the colored resin particles.

[0043] In addition, since the colored resin particles are spherical, a roll-to-roll process can be applied when manufacturing the light-adjusting laminate, and the manufacturing cost of the light-adjusting laminate can be reduced. The spherical shape is not limited to a perfect sphere, but also includes a nearly spherical shape, and includes a shape having an aspect ratio (major axis / minor axis) of 1.5 or less, for example.

[0044] From the viewpoints of improving practicality, making the gap appropriate, and effectively suppressing light leakage, the average particle diameter of the above-mentioned colored resin particles is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 10 μm or more, and is preferably 150 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less.

[0045] The particle diameter of the colored resin particles means the diameter when the colored resin particles are spherical, and means the diameter when the colored resin particles are assumed to be spherical with a volume equivalent thereto when the colored resin particles are other than spherical. The particle diameter of the colored resin particles is preferably the average particle diameter, and more preferably the number average particle diameter. The particle diameter of the colored resin particles can be measured by any particle size distribution measuring device. For example, it can be measured by using a particle size distribution measuring device using the principles of laser light scattering, electrical resistance value change, image analysis after imaging, etc. More specifically, as a method for measuring the particle diameter of the colored resin particles, a method of measuring the particle diameter of about 100,000 colored resin particles using a particle size distribution measuring device (Beckman Coulter's "Multisizer4") and calculating the average value can be mentioned.

[0046] From the viewpoint of controlling the gap between the substrates with even higher precision, the colored resin particles do not contain particles (colored resin particles) having a particle diameter of 1.2 times or more of the average particle diameter, or preferably contain particles (colored resin particles) having a particle diameter of 1.2 times or more of the average particle diameter at 1000 ppm or less. From the viewpoint of controlling the gap between the substrates with even higher precision, the content of particles (colored resin particles) having a particle diameter of 1.2 times or more of the average particle diameter is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 100 ppm or less, and particularly preferably 50 ppm or less. From the viewpoint of controlling the gap between the substrates with even higher precision, the content of particles (colored resin particles) having a particle diameter of 1.2 times or more of the average particle diameter is most preferably 0 ppm (not contained).

[0047] The content of particles (colored resin particles) having a particle size of 1.2 times or more the average particle size can be measured as follows: The colored resin particles are filtered through a filter with a pore size of 1.15 times the average particle size, the colored resin particles remaining on the filter are observed under an optical microscope, and the colored resin particles having a particle size of 1.2 times or more the average particle size are counted. The number of counted colored resin particles is divided by the total number of filtered colored resin particles to calculate the content of particles (colored resin particles) having a particle size of 1.2 times or more the average particle size.

[0048] From the viewpoint of controlling the gap between the substrates with even greater precision, the CV value of the particle diameter of the above-mentioned colored resin particles is preferably 2.0% or more, more preferably 2.5% or more, and is preferably 10% or less, more preferably 8.0% or less.

[0049] The CV value (coefficient of variation) of the particle size of the colored resin particles can be measured as follows.

[0050] CV value (%) = (ρ / Dn) × 100 ρ: Standard deviation of the particle size of the colored resin particles Dn: Average particle size of the above colored resin particles

[0051] From the viewpoint of controlling the gap between the substrates with even higher accuracy, the aspect ratio of the colored resin particles is preferably 1.5 or less, more preferably 1.3 or less. The aspect ratio indicates the major axis / minor axis. The aspect ratio is preferably determined by observing 10 arbitrary colored resin particles with an electron microscope or an optical microscope, taking the maximum diameter and the minimum diameter as the major axis and the minor axis, respectively, and calculating the average value of the major axis / minor axis of each spherical colored resin particle. The lower limit of the aspect ratio of the colored resin particles is not particularly limited. The aspect ratio of the colored resin particles may be 1.0 or more, or may be 1.1 or more.

[0052] From the viewpoint of improving the handleability of the obtained light-adjusting material and light-adjusting laminate, the specific gravity of the colored resin particles is preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less. The lower limit of the specific gravity of the colored resin particles is not particularly limited. The specific gravity of the colored resin particles may be 1.0 or more, or 1.1 or more.

[0053] The colored resin particles according to the present invention are preferably used as spacers. The colored resin particles according to the present invention are preferably used as spacers, particularly in light-control laminates. The colored resin particles may be used as spacers for light-control glass or may be used as spacers for light-control films. The colored resin particles are preferably used as spacers for light-control glass or light-control films.

[0054] Each component of the colored resin particles will be described in detail below.

[0055] <Resin particles> The colored resin particles include resin particles. The colored resin particles and the resin particles include a resin. The colored resin particles and the resin particles preferably include a polymer. The polymer is obtained by polymerizing a polymerization component. The colored resin particles and the resin particles preferably include a component derived from the polymerization component. The colored resin particles and the resin particles preferably include a polymer of the polymerization component.

[0056] Examples of the resin for forming the resin particles include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamideimide, polyether ether ketone, polyether sulfone, and divinylbenzene polymer. The divinylbenzene polymer may be a divinylbenzene copolymer. Examples of the divinylbenzene copolymer include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer. Since the 20% K value of the resin particles can be easily controlled within a suitable range, it is preferable that the resin for forming the resin particles is a polymer obtained by polymerizing one or more polymerizable monomers (polymerization components) having an ethylenically unsaturated group.

[0057] When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group includes a non-crosslinkable monomer and a crosslinkable monomer.

[0058] Examples of the non-crosslinkable monomer include vinyl compounds such as styrene monomers, α-methylstyrene, and chlorostyrene; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, and diethylene glycol divinyl ether; acid vinyl ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; (meth)acrylic compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, and the like. Examples of suitable (meth)acrylate compounds include alkyl (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; oxygen-containing (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, polyoxyethylene (meth)acrylate, and glycidyl (meth)acrylate; nitrile-containing monomers such as (meth)acrylonitrile; halogen-containing (meth)acrylate compounds such as trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate; α-olefin compounds such as diisobutylene, isobutylene, linearne, ethylene, and propylene; and conjugated diene compounds such as isoprene and butadiene.

[0059] Examples of the crosslinkable monomer include vinyl compounds such as vinyl monomers, such as divinylbenzene, 1,4-divinyloxybutane, and divinylsulfone; (meth)acrylic compounds such as polyfunctional (meth)acrylate compounds, such as tetramethylolmethane tetra(meth)acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate; Examples of the alkyl compounds include triallyl (iso) cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, and diallyl ether; examples of the silane compounds include silane alkoxide compounds such as tetramethoxysilane, tetraethoxysilane, triethylsilane, t-butyldimethylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, trimethoxysilylstyrene, γ-(meth)acryloxypropyltrimethoxysilane, 1,3-divinyltetramethyldisiloxane, methylphenyldimethoxysilane, and diphenyldimethoxysilane;Examples of the silane alkoxides include silanes containing polymerizable double bonds, such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, ethylmethyldivinylsilane, methylvinyldimethoxysilane, ethylvinyldimethoxysilane, methylvinyldiethoxysilane, ethylvinyldiethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; cyclic siloxanes such as decamethylcyclopentasiloxane; modified (reactive) silicone oils such as one-end modified silicone oil, both-end silicone oil, and side-chain silicone oil; and carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride.

[0060] The resin particles can be obtained by polymerizing the polymerizable monomer having the ethylenically unsaturated group. The polymerization method is not particularly limited, and the polymerization can be performed by a known method such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization, living radical polymerization, etc.

[0061] The resin particles can be easily obtained by carrying out radical polymerization using the polymerizable monomer having an ethylenically unsaturated group, etc. For example, the resin particles can be obtained by a method of suspension polymerization in the presence of a radical polymerization initiator, a seed polymerization method in which a monomer is swelled and polymerized together with a radical polymerization initiator using non-crosslinked seed particles, and a dispersion polymerization method.

[0062] From the viewpoint of controlling the gap between the substrates with higher accuracy, the polymerization component preferably contains a polyfunctional (meth)acrylate compound. That is, from the viewpoint of controlling the gap between the substrates with higher accuracy, the colored resin particles and the resin particles preferably contain a component derived from a polyfunctional (meth)acrylate compound.

[0063] The polyfunctional (meth)acrylate compound may be a bifunctional (meth)acrylate compound, a trifunctional (meth)acrylate compound, a trifunctional or higher (meth)acrylate compound, a tetrafunctional (meth)acrylate compound, or a tetrafunctional or higher (meth)acrylate compound. The polyfunctional (meth)acrylate compound may be used alone or in combination of two or more.

[0064] From the viewpoint of easily controlling the 20% K value of the colored resin particles within a suitable range, the colored resin particles and the resin particles preferably contain a difunctional (meth)acrylate compound or a trifunctional (meth)acrylate compound.

[0065] The polyfunctional (meth)acrylate compound is preferably polytetramethylene glycol di(meth)acrylate or dipentaerythritol tetra(meth)acrylate.

[0066] The content of the component derived from the polyfunctional (meth)acrylate compound in 100% by weight of the colored resin particles is preferably 10% by weight or more, more preferably 50% by weight or more, even more preferably 55% by weight or more, particularly preferably 60% by weight or more, and preferably 95% by weight or less, more preferably 90% by weight or less, and even more preferably 80% by weight or less. When the content of the component derived from the polyfunctional (meth)acrylate compound is the above lower limit or more and the above upper limit or less, the gap between the substrates can be controlled with even higher precision. From the viewpoint of controlling the gap between the substrates with even higher precision, it is preferable that the colored resin particles contain the component derived from the polyfunctional (meth)acrylate compound in an amount of 50% by weight or more in 100% by weight of the colored resin particles.

[0067] In 100% by weight of the resin particles, the content of the component derived from the polyfunctional (meth)acrylate compound is preferably 10% by weight or more, more preferably 50% by weight or more, even more preferably 60% by weight or more, particularly preferably 65% ​​by weight or more, and is preferably 95% by weight or less, more preferably 90% by weight or less, and even more preferably 80% by weight or less. When the content of the component derived from the polyfunctional (meth)acrylate compound is equal to or more than the lower limit and equal to or less than the upper limit, the gap between the substrates can be controlled with even higher precision.

[0068] <Coloring agent> The colored resin particles contain a colorant. The colorant may be disposed in the resin particles or on the surface of the resin particles. From the viewpoint of improving the electrical conductivity reliability of the obtained light-controlling laminate, the colorant is preferably disposed in the resin particles. The colorant is preferably contained in the resin particles.

[0069] The colorant may be inorganic particles, dyes, pigments, etc. The colorant may be used alone or in combination of two or more kinds.

[0070] Examples of the inorganic particles include carbon black particles, carbon nanotube particles, titanium black particles, graphene particles, iron oxide particles, zinc oxide particles, calcium carbonate particles, alumina particles, kaolin clay particles, calcium silicate particles, magnesium oxide particles, magnesium hydroxide particles, aluminum hydroxide particles, magnesium carbonate particles, talc particles, feldspar powder particles, mica particles, baryte particles, barium carbonate particles, titanium oxide particles, silica particles, and glass beads. The inorganic particles are preferably carbon black particles or titanium black particles.

[0071] The average particle size of the inorganic particles is preferably 0.01 μm or more, more preferably 0.5 μm or more, preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 10 μm or less. The average particle size indicates the weight average particle size. The average particle size can be measured by a dynamic light scattering method using a light scattering measuring device with a laser as a light source. An example of the light scattering measuring device is "DLS-6000AL" manufactured by Otsuka Electronics Co., Ltd.

[0072] Examples of the dye include pyrene-based dyes, aminoketone-based dyes, anthraquinone-based dyes, and azo-based dyes.

[0073] Examples of the pyrene-based dyes include Solvent Green 5 (CAS 79869-59-3) and Solvent Green 7 (CAS 6358-69-6).

[0074] Examples of the aminoketone dyes include Solvent Yellow 98 (CAS12671-74-8), Solvent Yellow 85 (CAS12271-01-1), Solvent Red 179 (CAS8910-94-5), and Solvent Red 135 (CAS71902-17-5).

[0075] Examples of the anthraquinone dyes include Solvent Yellow 163 (CAS13676091-0), Solvent Red 207 (CAS15958-69-6), Disperse Red 92 (CAS12236-11-2), Solvent Violet 13 (CAS81-48-1), Disperse Violet 31 (CAS6408-72-6), Solvent Blue 97 (CAS61969-44-6), Solvent Blue 45 (CAS37229-23-5), Solvent Blue 104 (CAS116-75-6) and Disperse Blue 214 (CAS104491-84-1).

[0076] Examples of the azo dyes include Solvent Yellow 30 (CAS 3321-10-4), Solvent Red 164 (CAS 70956-30-8), and Disperse Blue 146 (CAS 88650-91-3).

[0077] The colorant preferably contains a pigment. In this case, when used as a spacer, it is less likely to fade even when exposed to light for a long period of time, and light leakage can be suppressed for a long period of time. In addition, even if the colored resin particles are damaged and the colorant inside flows out, the occurrence of a short circuit can be suppressed. As a result, the electrical conductivity reliability of the obtained light-control laminate can be improved.

[0078] The pigment may be an organic pigment or an inorganic pigment. The organic pigment may have a metal atom or may not have a metal atom. The pigment may be a red pigment, a blue pigment, a yellow pigment, or a black pigment. Only one type of the pigment may be used, or two or more types may be used in combination.

[0079] From the viewpoints of more effectively suppressing light leakage over the long term, effectively suppressing discoloration, and increasing the conductive reliability of the obtained light-controlling laminate, it is more preferable that the pigment is an organic pigment, more preferably a black pigment, and even more preferably an organic black pigment.

[0080] Examples of the organic black pigment include anthraquinone pigments, anthanthrone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, flavanthrone pigments, diketopyrrolopyrrole pigments, quinacridone pigments, diketopyrrolopyrrole pigments, indigo / thioindigo pigments, perinone pigments, perylene pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, indoline pigments, isoindoline pigments, isoindolinone pigments, indanthrone pigments, dioxazine pigments, quinophthalone pigments, nickel azo pigments, metal complex pigments, azo pigments (insoluble azo pigments, soluble azo pigments, high molecular weight azo pigments, and azomethine azo black pigments), and aniline black pigments.

[0081] From the viewpoint of suppressing light leakage more effectively and for a long time and improving the electrical reliability of the obtained light-controlling laminate, the colorant preferably contains an organic black pigment, titanium black particles, or carbon black particles, more preferably contains an organic black pigment, and further preferably contains an azo pigment or a perylene pigment. 540 From the viewpoint of easily controlling * within a suitable range, the colorant preferably contains an azo pigment, titanium black particles, or carbon black particles.

[0082] The average particle size of the organic black pigment is preferably 1 nm or more, more preferably 10 nm or more, preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. The average particle size indicates the weight average particle size. The average particle size can be measured by a dynamic light scattering method using a light scattering measuring device with a laser as a light source. An example of the light scattering measuring device is "DLS-6000AL" manufactured by Otsuka Electronics Co., Ltd.

[0083] The colored resin particles preferably contain the colorant in an amount of 20% by weight or less in 100% by weight of the colored resin particles. In 100% by weight of the colored resin particles, the content of the colorant is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, and even more preferably 3.0% by weight or more, and is preferably 20% by weight or less, more preferably 15% by weight or less, and even more preferably 10% by weight or less. When the content of the colorant is equal to or more than the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is equal to or less than the upper limit, the insulation reliability of the colored resin particles can be more improved, and as a result, the conduction reliability of the obtained light-controlling laminate can be more improved. When the colored resin particles contain a plurality of colorants, the content of the colorant means the total content of the plurality of colorants.

[0084] <Other ingredients> The colored resin particles may contain other components as necessary. Examples of the other components include a polymerization initiator, a pigment dispersant, a resin particle dispersant, and a surfactant. The other components may be used alone or in combination of two or more.

[0085] (Light-control laminate) The light-controlling laminate according to the present invention includes a first substrate, a second substrate, and a light-controlling layer disposed between the first substrate and the second substrate. In the light-controlling laminate according to the present invention, the light-controlling layer includes the colored resin particles.

[0086] Since the light control laminate according to the present invention has the above-mentioned configuration, it is possible to control the gap between the substrates with high precision and to improve the electrical conductivity reliability of the obtained light control laminate.

[0087] The light control laminate may be a PDLC (Polymer Dispersed Liquid Crystal) type light control laminate or a SPD (Suspended Particle Device) type light control laminate. The light control laminate is preferably an SPD type or a PDLC type light control laminate. From the viewpoint of more effectively exerting the effects of the present invention, the light control laminate is more preferably a PDLC type light control laminate. The light control laminate does not have to be a liquid crystal display device.

[0088] The dimming laminate may or may not have a curved surface portion. The dimming laminate preferably has a curved surface portion. The dimming laminate may have a folded or curved shape. The dimming laminate preferably has a folded or curved shape, and is preferably used in a folded or curved shape. The dimming laminate may have a folded or curved portion. The dimming laminate, the first substrate, and the second substrate preferably have flexibility so that they can be folded or curved. When the dimming laminate has a curved portion, the curvature of the curved portion of the dimming laminate is preferably 300R or more and 1800R or less. Even if the dimming laminate has a curved portion or the curvature of the curved portion of the dimming laminate satisfies the above-mentioned preferred embodiment, the adhesive particles according to the present invention can be used to control the gap between the substrates with high precision throughout the dimming laminate and suppress light leakage.

[0089] The light-adjusting laminate is preferably used for a window glass or a partition of a vehicle. Examples of the vehicle include a car, a ship, and an aircraft. The light-adjusting laminate is preferably used for a window glass or a partition of a vehicle such as a vehicle, a ship, or an aircraft. The light-adjusting laminate is preferably a window glass or a partition, and more preferably a window glass or a partition of a vehicle such as a vehicle, a ship, or an aircraft. The light-adjusting laminate may be a window glass or a partition of a vehicle such as a vehicle, a ship, or an aircraft. The vehicle is preferably a transportation facility. The partition may be a member disposed between seats of the vehicle to separate the seats.

[0090] Next, specific embodiments of the present invention will be described with reference to the drawings.

[0091] FIG. 1 is a cross-sectional view that illustrates a colored resin particle according to a first embodiment of the present invention.

[0092] The colored resin particles 1 contain resin particles and a colorant. 2 When the lightness in the L*a*b* color system in accordance with JIS Z8781-4:2013 is measured for each of the colored resin particles after light irradiation with an integrated light amount of 10 ... 540 The ratio to * is 0.3 or more.

[0093] Fig. 2 is a cross-sectional view showing a PDLC type light control laminate containing colored resin particles according to the first embodiment of the present invention. Fig. 3 is a cross-sectional view showing a SPD type light control laminate containing colored resin particles according to the first embodiment of the present invention. Note that in Figs. 2 and 3, the size, thickness, shape, and amount of the light control layer and colored resin particles are appropriately changed from the actual size and shape for convenience of illustration.

[0094] The PDLC-type light-controlling laminate 11 shown in FIG. 2 includes a first substrate 2, a second substrate 3, and a light-controlling layer 4. The light-controlling layer 4 is sandwiched between the first substrate 2 and the second substrate 3. The light-controlling layer 4 is disposed between the first substrate 2 and the second substrate 3. A sealant may be disposed around the light-controlling layer 4 between the first substrate 2 and the second substrate 3.

[0095] The light-controlling layer 4 includes colored resin particles 1, liquid crystal capsules 4A, and a binder 4B. The liquid crystal capsules 4A are a liquid crystal material. The liquid crystal capsules 4A are dispersed in the binder 4B. The liquid crystal capsules 4A are held in the binder 4B in a capsule-like form. The liquid crystal material may be dispersed in the binder in a capsule-like form, or the liquid crystal material may be dispersed in the binder as a continuous phase.

[0096] The colored resin particles 1 are in contact with the first base material 2 and the second base material 3. The colored resin particles 1 control the gap between the first base material 2 and the second base material 3.

[0097] Electrodes (not shown) are formed on the surface of the first base material 2 and the surface of the second base material 3. Examples of materials for the electrodes include indium tin oxide (ITO). The electrodes are preferably transparent electrodes.

[0098] When no electric field is applied to the PDLC-type light control laminate 11, the orientation of the liquid crystal molecules in the liquid crystal capsules 4A is not uniform, and the difference in refractive index between the binder 4B and the liquid crystal material causes the incident light to be scattered in the binder 4B, resulting in an opaque state.

[0099] When an electric field is applied to the PDLC-type light control laminate 11, the liquid crystal molecules in the liquid crystal capsules 4A are aligned parallel to the electric field. In this state, the refractive indexes of the binder 4B and the liquid crystal material become equivalent, allowing light to pass through and resulting in a transparent state.

[0100] The SPD-type light-switching stack 21 shown in FIG. 3 includes a first substrate 2, a second substrate 3, and a light-switching layer 5. The light-switching layer 5 is sandwiched between the first substrate 2 and the second substrate 3. The light-switching layer 5 is disposed between the first substrate 2 and the second substrate 3.

[0101] The light control layer 5 includes colored resin particles 1, droplets 5A of a light control suspension, and a resin matrix 5B. The droplets 5A of the light control suspension are dispersed in the resin matrix 5B. The droplets 5A of the light control suspension are held in a droplet state in the resin matrix 5B.

[0102] The droplets 5A of the light control suspension contain a dispersion medium 5Aa and light control particles 5Ab. The light control particles 5Ab are dispersed in the dispersion medium 5Aa.

[0103] The colored resin particles 1 are in contact with the first base material 2 and the second base material 3. The colored resin particles 1 control the gap between the first base material 2 and the second base material 3.

[0104] Electrodes (not shown) are formed on the surface of the first base material 2 and the surface of the second base material 3. Examples of materials for the electrodes include indium tin oxide (ITO). The electrodes are preferably transparent electrodes.

[0105] When no electric field is applied to the SPD-type dimming stack 21, the incident light is absorbed, scattered, or reflected by the light control particles 5Ab due to Brownian motion of the light control particles 5Ab dispersed in the dispersion medium 5Aa that constitutes the droplets 5A of the light control suspension, and the incident light cannot pass through the dimming layer 5.

[0106] When an electric field is applied to the SPD type light control laminate 21, the light control particles 5Ab are aligned in a direction parallel to the electric field. Therefore, the incident light can pass between the aligned light control particles 5Ab and can be transmitted through the light control layer 5.

[0107] <Light-adjusting layer> The light-controlling layer preferably has a light-controlling property, which is a property that the visible light transmittance changes depending on the presence or absence of application of an electric field, thereby enabling the amount of incident light to be adjusted. The light-controlling layer contains the colored resin particles.

[0108] (PDLC method) The light-modulating layer preferably further comprises a binder and a liquid crystal material dispersed in the binder.

[0109] The liquid crystal material is not particularly limited, and may be any liquid crystal material as long as it has the property of changing its orientation by application of an electric field. The liquid crystal material may be dispersed in the binder as a continuous phase, or may be dispersed in the binder in the form of liquid crystal droplets or liquid crystal capsules. Examples of the liquid crystal material include nematic liquid crystals and cholesteric liquid crystals.

[0110] Examples of the nematic liquid crystal material include cyanobiphenyls, phenyl esters, azoxybenzenes, fluorine-containing biphenyls, carbonates, Schiff bases, etc. The nematic liquid crystal material may be used alone or in combination of two or more.

[0111] Examples of the cholesteric liquid crystal material include nematic liquid crystals and smectic liquid crystals such as steroid cholesterol derivatives, Schiff bases, azos, azoxys, benzoates, biphenyls, terphenyls, cyclohexyl carboxylates, phenylcyclohexanes, biphenylcyclohexanes, pyrimidines, dioxanes, cyclohexylcyclohexane esters, cyclohexylethanes, cyclohexanes, tolanes, alkenyls, stilbenes, and condensed polycyclics, and materials obtained by adding chiral components made of optically active materials such as Schiff bases, azos, esters, and biphenyls to mixed liquid crystals. Only one type of cholesteric liquid crystal material may be used, or two or more types may be used in combination.

[0112] The binder holds the liquid crystal material and suppresses the flow of the liquid crystal material. The binder is not particularly limited as long as it is not dissolved in the liquid crystal material, has a strength capable of withstanding an external force, and has high transmittance to reflected light and incident light. Examples of the binder material include water-soluble polymer materials such as gelatin, polyvinyl alcohol, cellulose derivatives, polyacrylic acid polymers, ethyleneimine, polyethylene oxide, polyacrylamide, polystyrene sulfonate, polyamidine, and isoprene-based sulfonic acid polymers, and materials that can be made into aqueous emulsions such as fluorine resins, silicone resins, acrylic resins, urethane resins, and epoxy resins. Only one type of binder material may be used, or two or more types may be used in combination.

[0113] The binder is preferably crosslinked by a crosslinking agent. The crosslinking agent is not particularly limited as long as it forms a crosslink between the binders and hardens, makes the binder difficult to dissolve, or makes it insoluble. Examples of the crosslinking agent include acetaldehyde, glutaraldehyde, glyoxal, potassium alum hydrate of a polyvalent metal salt compound, adipic acid dihydrazide, melamine formalin oligomer, ethylene glycol diglycidyl ether, polyamide epichlorohydrin, and polycarbodiimide. The crosslinking agent may be used alone or in combination of two or more.

[0114] (SPD method) The light control layer preferably further comprises a resin matrix and a light control suspension dispersed in the resin matrix.

[0115] The light control suspension includes a dispersion medium and light control particles dispersed in the dispersion medium.

[0116] The light control particles include carbon-based materials such as polyiodides and carbon black, metal materials such as copper, nickel, iron, cobalt, chromium, titanium, and aluminum, and inorganic compound materials such as silicon nitride, titanium nitride, and aluminum oxide. These materials may also be particles coated with a polymer. The light control particles may be used alone or in combination of two or more kinds.

[0117] The dispersion medium disperses the light control particles in a flowable state. The dispersion medium is preferably a material that selectively adheres to the light control particles, covers the light control particles, and acts to move the light control particles to the phase-separated droplet phase during phase separation with the resin matrix, and has no electrical conductivity and no affinity with the resin matrix. Furthermore, the dispersion medium is preferably a liquid copolymer that has a refractive index similar to that of the resin matrix when made into a light control laminate. As the liquid copolymer, a (meth)acrylic acid ester oligomer having a fluoro group or a hydroxyl group is preferable, and a (meth)acrylic acid ester oligomer having a fluoro group and a hydroxyl group is more preferable. When such a copolymer is used, the monomer unit of the fluoro group or the hydroxyl group faces the light control particles, and the remaining monomer unit stabilizes the droplets of the light control suspension in the resin matrix. For this reason, the light control particles are easily dispersed in the light control suspension, and the light control particles are easily guided into the droplets that are phase-separated during phase separation with the resin matrix.

[0118] Examples of the (meth)acrylic acid ester oligomer having a fluoro group or a hydroxyl group include 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 3,5,5-trimethylhexyl acrylate / 2-hydroxypropyl acrylate / fumaric acid copolymer, butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl acrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl ... , 1H,2H,2H-heptadecafluorodecyl / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 1H,1H,5H-octafluoropentyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, and 1H,1H,2H,2H-heptadecafluorodecyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer. It is more preferable that these (meth)acrylic acid ester oligomers have both a fluoro group and a hydroxyl group.

[0119] The weight average molecular weight of the (meth)acrylic acid ester oligomer is preferably 1,000 or more, more preferably 2,000 or more, and is preferably 20,000 or less, more preferably 10,000 or less.

[0120] The light control layer can be produced using a resin material for forming the resin matrix and the light control suspension.

[0121] The resin material is preferably a resin material that is cured by irradiation with energy rays. Examples of the resin material that is cured by irradiation with energy rays include a polymer composition containing a photopolymerization initiator and a polymer compound that is cured by energy rays such as ultraviolet rays, visible rays, and electron beams. Examples of the polymer composition include a polymer composition containing a polymerizable monomer having an ethylenically unsaturated group and a photopolymerization initiator. Examples of the polymerizable monomer having an ethylenically unsaturated group include a non-crosslinkable monomer and a crosslinkable monomer.

[0122] The non-crosslinkable monomer may be the non-crosslinkable monomer described above.The crosslinkable monomer may be the crosslinkable monomer described above.

[0123] Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-(4-(2-hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and (1-hydroxycyclohexyl)phenyl ketone.

[0124] The resin material may contain an organic solvent-soluble resin, a thermoplastic resin, poly(meth)acrylic acid, etc. The resin material may also contain various additives such as a coloring inhibitor, an antioxidant, and an adhesion imparting agent, and may also contain a solvent.

[0125] <First substrate and second substrate> The first substrate is preferably a transparent substrate. The second substrate is preferably a transparent substrate. The transparent substrate is, for example, a substrate having light transparency (light-transmitting substrate). For example, light is transmitted from one side of the transparent substrate to the other side through the transparent substrate. For example, when a substance on the other side of the transparent substrate is viewed from one side of the transparent substrate through the transparent substrate, the substance can be seen. Transparent includes, for example, translucency. The transparent substrate may be colorless and transparent, or colored and transparent.

[0126] The materials of the first and second substrates are not particularly limited. The materials of the first and second substrates may be the same or different. Examples of the materials of the first and second substrates include glass and resin films. Examples of the glass include soda-lime glass for general construction, lead glass, borosilicate glass, and glass of various compositions for other applications, as well as functional glass such as heat-reflecting glass, heat-absorbing glass, and reinforced glass. Examples of the resin film include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, and resin films such as acrylic resin films. Because of their excellent transparency, formability, adhesion, and processability, the first and second substrates are preferably resin substrates, more preferably resin films, and even more preferably polyethylene terephthalate films.

[0127] The first and second substrates preferably include a substrate body and a conductive film formed on the surface of the substrate body so that an electric field for dimming can be applied. Examples of the conductive film include indium tin oxide (ITO), SnO2, and In2O3. The conductive film is preferably a transparent conductive film.

[0128] From the viewpoint of further increasing the visibility of the light-control laminate, the visible light transmittance of the first substrate and the second substrate is preferably 75% or more, and more preferably 80% or more.

[0129] The visible light transmittance of the first substrate and the second substrate can be measured by spectroscopic measurement or the like in accordance with ISO13837:2008.

[0130] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0131] The following materials were prepared:

[0132] (Coloring agent): Carbon black (inorganic black pigment) Titanium Black (inorganic black pigment) Azo pigments (organic black pigments)

[0133] (Resin particle material): styrene Divinylbenzene (purity 96% by weight, "DVB960" manufactured by Nippon Steel Chemical & Material Co., Ltd.) Polytetramethylene glycol diacrylate (polyfunctional (meth)acrylate compound, Kyoeisha Chemical Co., Ltd. "PTMGA250") Pentaerythritol tetraacrylate (multifunctional (meth)acrylate compound, "A-TMMT" manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0134] (1) Preparation of colored resin particles Example 1 5 parts by weight of carbon black was added to 30 parts by weight of divinylbenzene and 70 parts by weight of polytetramethylene glycol diacrylate, and the mixture was stirred to obtain a monomer mixture. 2000 parts by weight of a 2.5% by weight aqueous solution of polyvinyl alcohol with a molecular weight of about 2000 dissolved in pure water was placed in a reaction vessel. The obtained monomer mixture was placed in the mixture and stirred to adjust the particle size of the monomer droplets to a predetermined particle size. Next, the mixture was heated at 90°C for 9 hours to polymerize the monomer droplets, and particles were obtained. The obtained particles were washed several times with hot water and acetone, and then classified to recover colored resin particles.

[0135] (Examples 2 to 15) Colored resin particles were produced in the same manner as in Example 1, except that the materials and contents (wt %) of the colorant and resin particles were changed as shown in Tables 1 to 4.

[0136] Comparative Example 1 Resin particles were produced in the same manner as in Example 1, except that the material and content (wt %) of the resin particles were changed as shown in Table 4. In Comparative Example 1, no colorant was used.

[0137] For the colored resin particles of Examples 1 to 15 and the resin particles of Comparative Example 1, the following light-control laminates were produced.

[0138] (2) Preparation of light-control laminate SPD photochromic stack: A light-control film was produced in which a known SPD layer was arranged between two sheets of PET film on which transparent and conductive ITO was vapor-deposited, except that the obtained colored resin particles or the resin particles of Comparative Example 1 were dispersed at 5% by weight. An SPD-type light-control laminate was produced by sandwiching the light-control film between two sheets of transparent glass.

[0139] PDLC light control stack: A light-control film was produced in which a known PDLC layer was arranged between two sheets of PET film on which transparent and conductive ITO was vapor-deposited, except that the obtained colored resin particles or the resin particles of Comparative Example 1 were dispersed at 5% by weight. A PDLC-type light-control laminate was produced by sandwiching the light-control film between two sheets of transparent glass.

[0140] (evaluation) (1) Average particle diameter The particle sizes of about 100,000 particles were measured for the obtained colored resin particles and the resin particles of Comparative Example 1 using a particle size distribution measuring device (Beckman Coulter's "Multisizer 4") to measure the average particle size and standard deviation. In addition, the content (ppm) of particles (colored resin particles or resin particles) having a particle size 1.2 times or more the average particle size was measured using the method described above.

[0141] (2) CV value of particle size For the obtained colored resin particles and the resin particles of Comparative Example 1, the CV value of the particle size was calculated by the method described above.

[0142] (3) Specific gravity The specific gravity of the obtained colored resin particles and the resin particles of Comparative Example 1 was measured using an "AccuPyc II 1345 Series" manufactured by Shimadzu Corporation.

[0143] (4) Brightness 100 mg of the obtained colored resin particles and the resin particles of Comparative Example 1 were thinly spread on an adhesive tape (length 75 mm, width 15 mm) attached to a slide glass, and air was blown for 30 seconds to prepare a sample carrying the colored resin particles. The sample was then irradiated with 255 W / m 2 of a Sunshine carbon arc lamp. 2 588 hours at illuminance of 540MJ / m 2 The light was measured for 10 arbitrary points of the sample before and after the light irradiation using a color difference meter ("TES-3250" manufactured by SATOTECH Co., Ltd.) with a measurement range of a circle having a diameter of 8 mm, and the average values ​​were designated as lightness L0* and lightness L 540 *. In addition, the ratio (L0* / L 540 *) was requested.

[0144] (5) 20% K value For the obtained colored resin particles and the resin particles of Comparative Example 1, the 20% K value was measured using Fisherscope H-100 manufactured by Fisher Instruments by the method described above.

[0145] (6) Light leakage prevention The obtained colored resin particles were used as spacers for a TN (twisted nematic) type liquid crystal display element, and a TN type liquid crystal display element was produced by the following method.

[0146] A SiO2 film was deposited on one side of the first and second transparent substrates (transparent glass plates, 150 mm x 150 mm) by CVD, and then an ITO film was formed on the entire surface of the SiO2 film by sputtering. A polyimide alignment film (Nissan Chemical's "SE-7210") was then placed by spin coating, and baked at 280°C for 90 minutes to form a polyimide alignment film. Next, after a rubbing treatment, the obtained colored resin particles were spread on the alignment film side of the first transparent substrate to a thickness of 1 mm using a dry spreader (Nisshin Engineering's "DISPA-μR"). 2The particles were dispersed so that there were 20 to 100 particles per cell. After forming a peripheral sealant (main agent: SE4500, hardener: HAVEN CHEMICAL Co., Ltd.) around the periphery of the second transparent substrate, the substrates were arranged facing each other so that the rubbing direction (twist angle) was 90°, and the first transparent substrate and the second transparent substrate were bonded together. The sealant was hardened by treating at 160°C for 90 minutes to prepare an empty cell. After injecting TN type liquid crystal (Merck Co., Ltd.'s "MLC-6222") into the obtained empty cell, the injection port was sealed with an adhesive (Sekisui Chemical Co., Ltd.'s "Photolec A-780") to prepare a TN type liquid crystal display element, which was then heat-treated at 120°C for 30 minutes.

[0147] The obtained TN type liquid crystal display element was sandwiched between polarizing films arranged in a cross Nicol arrangement so as to be in a normally white display mode, and a voltage of 7 V was applied while observing the state of light leakage of the colored resin particles using a digital microscope (Keyence Corporation, "VHX-2000"). The image magnification was set to 200 times, and the ratio of the number of colored resin particles with light leakage was calculated in any five visual fields. The same calculation was also performed for the resin particles of Comparative Example 1. The light leakage suppression property was evaluated according to the following criteria.

[0148] [Criteria for light leakage suppression] XX: The percentage of colored resin particles with light leakage is less than 1% ○: The percentage of colored resin particles with light leakage is 1% or more and less than 3%. △: The percentage of colored resin particles with light leakage is 3% or more and less than 5% ×: The percentage of colored resin particles with light leakage is 5% or more.

[0149] (7) Fracture suppression properties of colored resin particles In the obtained light-control laminate, 2 After applying pressure at 1000 rpm for 10 minutes, the particles were observed using a digital microscope (Keyence Corporation's "VHX-2000") and the percentage of the number of broken colored resin particles was calculated. The breakage suppression properties of the colored resin particles were evaluated according to the following criteria.

[0150] [Criteria for determining fracture resistance of colored resin particles] ○○: The percentage of destroyed colored resin particles is less than 0.01% ○: The percentage of destroyed colored resin particles is 0.01% or more and less than 0.1% △1: The percentage of destroyed colored resin particles is 0.1% or more and less than 0.5% △2: The percentage of destroyed colored resin particles is 0.5% or more and less than 1.0% ×: The percentage of destroyed colored resin particles is 1.0% or more.

[0151] (8) Conduction reliability of the light-control laminate The connection resistance between the upper and lower electrodes of the obtained light-control laminate was measured using a four-terminal method, and the average connection resistance was calculated. Note that, based on the relationship of voltage = current x resistance, the connection resistance can be calculated by measuring the voltage when a constant current is passed through it. The electrical reliability of the light-control laminate was evaluated according to the following criteria.

[0152] [Criteria for determining the electrical reliability of light-control laminates] ○○: Connection resistance is 1.0×10 10 Ω / □ or more ○: Connection resistance is 1.0×10 9 Ω / □ or more, 1.0×10 10 Less than Ω / □ △1: Connection resistance is 1.0×10 8 Ω / □ or more, 1.0×10 9 Less than Ω / □ △2: Connection resistance is 1.0×10 7 Ω / □ or more, 1.0×10 8 Less than Ω / □ ×: Connection resistance is 1.0×10 7 Less than Ω / □

[0153] (9) Gap controllability For the obtained light-controlling laminate, the maximum and minimum values ​​of the distance between the substrates (transparent glass) were measured, and the gap controllability was evaluated according to the following criteria.

[0154] [Gap control criteria] ○○: The maximum distance between the substrates is less than 1.05 times the minimum distance. ○: The maximum distance between the substrates is 1.05 times or more and less than 1.10 times the minimum distance. △1: The maximum distance between the substrates is 1.10 times or more and less than 1.15 times the minimum distance. △2: The maximum distance between the substrates is 1.15 times or more and less than 1.20 times the minimum distance. ×: The maximum distance between the substrates is 1.20 times or more the minimum distance.

[0155] The compositions of the colored resin particles and the results are shown in Tables 1 to 4 below.

[0156] [Table 1]

[0157] [Table 2]

[0158] [Table 3]

[0159] [Table 4]

[0160] In addition, since no colorant was included in Comparative Example 1, (7) the fracture suppression ability of the colored resin particles, (8) the conduction reliability of the light-controlling laminate, and (9) the gap controllability were not evaluated. [Explanation of symbols]

[0161] 1...Colored resin particles 2...First substrate 3...Second substrate 4,5…Photochromic layer 4A…Liquid crystal capsule 4B…Binder 5A…droplet of light-adjusting suspension 5Aa…Dispersion medium 5Ab…Light adjustment particle 5B…Resin matrix 11...PDLC type light control laminate 21…SPD type light control laminate

Claims

1. Contains resin particles and a colorant, Colored resin particles before light irradiation and 540 MJ / m ２ When the lightness in the L*a*b* color system in accordance with JIS Z8781-4:2013 was measured for each of the colored resin particles after light irradiation with light at an integrated light amount of Lightness L of colored resin particles before light irradiation ０ * is 60 or less, the lightness L 540 * of the colored resin particles after light irradiation is 1 or more and 60 or less; Lightness L of colored resin particles before light irradiation ０ * The lightness L of the colored resin particles after light irradiation ５４０ *Colored resin particles having a ratio of 0.3 or more.

2. 20% K value is 100N / mm ２ More than 5000N / mm ２ 2. The colored resin particles according to claim 1, wherein:

3. Volume resistivity is 1.0 × 10 ９ The colored resin particles according to claim 1 or 2, having a viscosity of Ω·cm or more.

4. 3. The colored resin particles according to claim 1, wherein the average particle size is from 1 μm to 150 μm.

5. 3. The colored resin particles according to claim 1, which do not contain particles having a particle diameter of 1.2 times or more the average particle diameter, or which contain particles having a particle diameter of 1.2 times or more the average particle diameter in an amount of 1000 ppm or less.

6. 3. The colored resin particles according to claim 1, wherein the CV value of the particle diameter is 10% or less.

7. The colored resin particles according to claim 1 or 2, wherein the colorant comprises an organic black pigment, titanium black particles, or carbon black particles.

8. 3. The colored resin particles according to claim 1, wherein the colored resin particles contain the colorant in an amount of 20% by weight or less based on 100% by weight of the colored resin particles.

9. 3. The colored resin particles according to claim 1, which have a specific gravity of 1.5 or less.

10. The colored resin particles according to claim 1 or 2, wherein the colored resin particles contain a component derived from a polyfunctional (meth)acrylate compound.

11. 3. The colored resin particles according to claim 1, wherein the colored resin particles contain a component derived from a polyfunctional (meth)acrylate compound in an amount of 50% by weight or more relative to 100% by weight of the colored resin particles.

12. The colored resin particles according to claim 1 or 2, which are used as spacers.

13. The colored resin particles according to claim 12 , which are used as spacers in a light-control laminate.

14. The light-transmitting device includes a first substrate, a second substrate, and a light-control layer disposed between the first substrate and the second substrate; A light-control laminate, wherein the light-control layer comprises the colored resin particles according to claim 1 .

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