Resin particles and light control laminate

Abstract

The purpose of the present invention is to provide resin particles having high weather resistance.　When resin particles (1) according to the present invention are subjected to a weather resistance test under the conditions of 85°C, 50%RH, an illuminance of 255 W / m2, and 500 hours using a sunshine carbon arc lamp, the ratio of the compression recovery rate of the resin particles (1) at 20% compressive deformation after the weather resistance test to the compression recovery rate of the resin particles at 20% compressive deformation before the weather resistance test is 0.50 or more.

Description

Resin particles and light-control laminate

[0001] The present invention relates to resin particles and uses thereof. The present invention also relates to a light-control laminate using the resin particles.

[0002] Light-control materials such as light-control glass and light-control films have the property of changing light transmittance depending on whether an electric field is applied or not, making it possible to adjust the amount of incident light. Depending on the mechanism by which light transmittance is changed, light-control materials are broadly classified into suspended particle device (SPD) systems, polymer dispersed liquid crystal (PDLC) systems, and guest-host liquid crystal (GHLC) systems.

[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 incident light does not pass through the light-modulating 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 incident light passes through the light-modulating material. In this way, the SPD method can adjust light transmittance by utilizing the polarization orientation of the light control particles.

[0004] The PDLC method is a method in which liquid crystals are dispersed in a resin matrix. PDLC methods include a method in which the liquid crystal and resin matrix are dispersed as a continuous phase, and a method in which the liquid crystal is dispersed as liquid crystal capsules in a resin matrix. When no electric field is applied, the liquid crystal molecules are not uniformly oriented, and the difference in refractive index between the resin matrix and the liquid crystal causes incident light to scatter within the light-adjusting material, resulting in an opaque state. When an electric field is applied, the liquid crystal molecules align 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 incident light to pass through the light-adjusting material, resulting in a transparent state. In this way, the PDLC method adjusts light transmittance by utilizing the molecular orientation of the liquid crystal.

[0005] The GHLC method dissolves a dichroic dye with a high aspect ratio in liquid crystal. In the GHLC method, when no electric field is applied, the liquid crystal molecules are oriented perpendicular to the incident light due to the orientation control of the alignment film. Therefore, the incident light is absorbed by the dichroic dye, which is also oriented perpendicularly, resulting in an extremely low transmittance state. When an electric field is applied, the liquid crystal molecules align parallel to the electric field. At this time, the dichroic dye is also oriented parallel to the incident light, allowing the incident light to transmit, resulting in a transparent state. In this way, the GHLC method adjusts the light transmittance by controlling the molecular orientation of the liquid crystal and dichroic dye.

[0006] When a light-controlling laminate is produced using a light-controlling material, spacers may be used to control the gap between two substrates. Examples of the spacers include resin particles. As an example of a method for producing such resin particles, Patent Document 1 below discloses a method for producing colored particles in which polymer particles obtained by polymerizing a crosslinkable monomer having two or more unsaturated double bonds and a non-crosslinkable monomer having one unsaturated double bond in a specific weight ratio are dyed in a supercritical fluid or a subcritical fluid.

[0007] Japanese Patent Application Laid-Open No. 2006-257180

[0008] Light-control laminates are sometimes used in in-vehicle components, building materials (for example, window glass for automobiles and buildings, blind curtains), helmets, sunglasses, and the like, for the purpose of blocking light such as sunlight.

[0009] However, in the conventional resin particles described in Patent Document 1, when the resin particles are used as spacers and the resin particles between two substrates are irradiated with light for a long period of time (e.g., 500 hours or more), the resin particles may be altered, making it impossible to adequately control the gap between the two substrates. As a result, there is a problem that the resulting light-control laminate may exhibit display unevenness. In other words, there is a problem that the conventional resin particles cannot sufficiently improve weather resistance.

[0010] An object of the present invention is to provide resin particles having high weather resistance and uses thereof, and a light-control laminate using the resin particles.

[0011] This specification discloses the following resin particles, uses thereof, and light-control laminates.

[0012] Item 1. Using a Sunshine carbon arc lamp, 85°C, 50% RH, illuminance 255 W / m ２ and 500 hours, the ratio of the compression recovery rate of the resin particles at 20% compressive deformation after the weather resistance test to the compression recovery rate of the resin particles at 20% compressive deformation before the weather resistance test is 0.50 or more.

[0013] Item 2. The resin particles according to Item 1, wherein the resin particles have a dielectric strength of 10 kV / mm or more.

[0014] Item 3. The resin particles according to Item 1 or 2, wherein the resin particles have a compression recovery rate of 30% or more after a 20% compressive deformation before the weather resistance test.

[0015] Item 4. The resin particles according to any one of items 1 to 3, wherein the resin particles have a sphericity of 0.55 to 0.98 when sandwiched between two substrates at a pressure of 0.1 MPa.

[0016] Item 5. The resin particles according to any one of Items 1 to 4, which contain a colorant.

[0017] Item 6. The resin particles according to Item 5, wherein the colorant has a particle diameter of 500 nm or less.

[0018] Item 7. The resin particles according to Item 5 or 6, wherein the colorant includes carbon black, titanium black, manganese oxide, an organic black pigment, or an organic black dye.

[0019] Item 8. The resin particles according to any one of Items 1 to 7, wherein the resin particles have a static angle of repose of 2° or more and 60° or less.

[0020] Item 9. The resin particles according to any one of Items 1 to 8, wherein the particle diameter of the resin particles is 1 μm or more and 150 μm or less.

[0021] Item 10. The 20% compressive elastic modulus of the resin particles is 1 N / mm ２ More than 5000N / mm ２ Item 10. The resin particles according to any one of items 1 to 9, wherein:

[0022] Item 11. The resin particle according to any one of Items 1 to 10, comprising a base particle and a coating layer disposed on the surface of the base particle.

[0023] Item 12. The resin particles according to Item 11, wherein the coating layer has a thickness of 30 nm or more and 500 nm or less.

[0024] Item 13. The resin particles according to Item 11 or 12, wherein the material of the coating layer contains a compound having an aromatic skeleton, a compound having a hydrocarbon group with three or more carbon atoms in the main chain, or a silicon atom.

[0025] Item 14. The resin particles according to any one of Items 1 to 13, having an uneven surface.

[0026] Item 15. The resin particles according to any one of Items 1 to 14, which are used as a spacer.

[0027] Item 16. The resin particles according to Item 15, which are used as spacers in a light-control laminate.

[0028] Item 17. A light-control laminate comprising a first substrate, a second substrate, and a light-control layer disposed between the first substrate and the second substrate, wherein the light-control layer contains the resin particles according to any one of items 1 to 16.

[0029] Item 18. The light control laminate according to Item 17, which is a light control laminate other than a liquid crystal display device.

[0030] Item 19. The light-control laminate according to Item 17 or 18, which is a polymer-dispersed liquid crystal type light-control laminate, a suspended particle device type light-control laminate, or a guest-host liquid crystal type light-control laminate.

[0031] Item 20. A light-control laminate including a first substrate, a second substrate, and a light-control layer disposed between the first substrate and the second substrate, wherein the resin particles according to any one of items 1 to 16 are used in the light-control layer.

[0032] The resin particles according to the present invention are heated using a sunshine carbon arc lamp at 85°C, 50% RH, and an illuminance of 255 W / m ２ When a weather resistance test is conducted under the conditions of 1000 hours, 1000 hours, and 500 hours, the ratio of the compressive recovery rate of the resin particles after the weather resistance test at 20% compressive deformation to the compressive recovery rate of the resin particles before the weather resistance test at 20% compressive deformation is 0.50 or more. Since the resin particles according to the present invention have the above-mentioned configuration, the weather resistance of the resin particles can be improved.

[0033] FIG. 1 is a cross-sectional view schematically showing resin particles according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing resin particles according to a second embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing resin particles according to a third embodiment of the present invention. FIG. 4 is a cross-sectional view schematically showing a PDLC-type light-control stack including resin particles according to the first embodiment of the present invention. FIG. 5 is a cross-sectional view schematically showing an SPD-type light-control stack including resin particles according to the first embodiment of the present invention. FIG. 6 is a cross-sectional view schematically showing a GHLC-type light-control stack including resin particles according to the first embodiment of the present invention.

[0034] 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".

[0035] (Resin Particles) The resin particles according to the present invention are formed by heating at 85°C, 50% RH, and an illuminance of 255 W / m using a sunshine carbon arc lamp. ２ and 500 hours, the ratio of the compressive recovery rate of the resin particles at 20% compressive deformation after the weather resistance test to the compressive recovery rate of the resin particles at 20% compressive deformation before the weather resistance test is 0.50 or more.

[0036] The resin particles according to the present invention have the above-described configuration. Even when the resin particles are used as spacers and the resin particles between two substrates are irradiated with light for a long period of time (e.g., 500 hours or more), the decrease in the compression recovery rate of the resin particles can be suppressed, and the gap between the substrates can be controlled with high precision. As a result, the occurrence of display unevenness in the resulting light-controlling laminate can be suppressed. That is, the resin particles according to the present invention can improve the weather resistance of the resin particles. A light-controlling laminate using the resin particles according to the present invention can achieve a uniform display when no electric field is applied, and can also achieve a uniform display when an electric field is applied. In particular, in light-controlling laminates other than liquid crystal display devices, display unevenness is significantly more visible when an electric field is applied and light transmittance is increased. However, the use of the resin particles according to the present invention can significantly reduce display unevenness when an electric field is applied and light transmittance is increased.

[0037] In this specification, the ratio of the compression recovery rate of resin particles after the weathering test at 20% compression deformation to the compression recovery rate of resin particles before the weathering test at 20% compression deformation is referred to as the ratio (compression recovery rate of resin particles after the weathering test at 20% compression deformation / compression recovery rate of resin particles before the weathering test at 20% compression deformation).The ratio (compression recovery rate of resin particles after the weathering test at 20% compression deformation / compression recovery rate of resin particles before the weathering test at 20% compression deformation) is preferably 0.55 or more, more preferably 0.60 or more, even more preferably 0.65 or more, particularly preferably 0.70 or more.When the ratio (compression recovery rate of resin particles after the weathering test at 20% compression deformation / compression recovery rate of resin particles before the weathering test at 20% compression deformation) is above the lower limit, the effects of the present invention can be more effectively exhibited. The upper limit of the ratio (compression recovery rate of resin particles at 20% compressive deformation after weather resistance test / compression recovery rate of resin particles at 20% compressive deformation before weather resistance test) is not particularly limited. The ratio (compression recovery rate of resin particles at 20% compressive deformation after weather resistance test / compression recovery rate of resin particles at 20% compressive deformation before weather resistance test) may be 1.50 or less, 1.30 or less, or 1.00 or less. The range of the ratio (compression recovery rate of resin particles at 20% compressive deformation after weather resistance test / compression recovery rate of resin particles at 20% compressive deformation before weather resistance test) can be set by appropriately selecting the lower limit and the upper limit.

[0038] The above ratio (compression recovery rate of resin particles after 20% compressive deformation after weather resistance test / compression recovery rate of resin particles after 20% compressive deformation before weather resistance test) can be measured, for example, as follows: In accordance with JIS B7753:2004, using a sunshine carbon arc lamp, at 85°C, 50% RH, with a wavelength of 300 nm to 700 nm and an illuminance of 255 W / m ２ and 500 hours (cumulative light intensity: 459 MJ / m ２) and conduct a weather resistance test. As the Sunshine Carbon Arc Lamp (Sunshine Carbon Arc Weather-Ometer (SWOM)), for example, the "Sunshine Carbon Arc (Open Frame Carbon Arc) Lamp Type Light Fastness and Weather Resistance Tester: WEL-300L" manufactured by Suga Test Instruments Co., Ltd. may be used. Because there is a possibility that the resin particles may be scattered by the air flow inside the weather resistance tester during the weather resistance test, it is desirable to prepare a test piece as follows and conduct the weather resistance test. Ten resin particles are scattered on a 5 cm square optical glass (thickness: 0.7 mm, "BK-7" manufactured by Hiraoka Special Glass Manufacturing Co., Ltd., double-sided polished). Next, a 1 mm wide adhesive is applied around the periphery of the optical glass on which the resin particles have been scattered, and the same optical glass is placed on top to sandwich the resin particles between the two optical glasses, thereby obtaining a laminate. A 100 g weight is placed on the resulting laminate and allowed to stand for 5 minutes. After standing, the weight is removed to obtain a test piece. The resulting test piece is used in a weather resistance test. When placing the test piece inside the weather resistance tester, aluminum tape is used to secure only the adhesive portion around the test piece, thereby preventing deterioration of the adhesive and leakage of resin particles from the test piece during the weather resistance test. After the weather resistance test, the optical glass on the top of the test piece is removed, and the resin particles remaining on the optical glass on the bottom are used to measure the compression recovery rate after the weather resistance test. The compression recovery rate of the resin particles before and after the weather resistance test is measured using the following method. Resin particles are scattered on a sample stage. Using a microcompression tester, a load (reverse load value) is applied to each scattered resin particle at 25°C toward the center of the resin particle with the end face of a smooth cylindrical indenter (100 μm diameter, made of diamond) until the resin particle is compressed and deformed by 20%. Thereafter, the load is removed until the load value for the origin (0.20 mN) is reached. The load-compression displacement during this period is measured, and the compression recovery rate can be calculated using the following formula. The loading rate is 0.33 mN / sec. This measurement is performed on five resin particles, and the average value of the five measured values ​​is taken as the compression recovery rate. As the microcompression tester, for example, the "Fisherscope H-100" manufactured by Fischer and the "ENT-NEXUS" manufactured by Elionix can be used.

[0039] Compression recovery rate (%) = (L2 / L1) x 100 L1: Compression displacement from the load value for origin when applying a load to the reverse load value L2: Unloading displacement from the reverse load value when releasing the load to the load value for origin

[0040] The compression recovery rate of the resin particles after 20% compression deformation before the weather resistance test is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, even more preferably 80% or more, particularly preferably more than 80%, most preferably 81% or more, and preferably 99% or less, more preferably 98% or less, and even more preferably 95% or less. When the compression recovery rate of the resin particles after 20% compression deformation before the weather resistance test is equal to or greater than the lower limit, the gap between the substrates can be controlled with high precision, and the occurrence of initial display unevenness in the resulting light-controlling laminate can be suppressed. When the compression recovery rate of the resin particles after 20% compression deformation before the weather resistance test is equal to or less than the upper limit, even when a flexible substrate such as a PET film is used in the production of the light-controlling laminate, scratches on the surface of the substrate can be suppressed, and the visibility of the resulting light-controlling laminate can be improved.

[0041] The compression recovery rate of the resin particles after the weather resistance test under 20% compression deformation is preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, particularly preferably 70% or more, and is preferably 98% or less, more preferably 97% or less, and even more preferably 95% or less. When the compression recovery rate of the resin particles after the weather resistance test under 20% compression deformation is the lower limit or more, the effects of the present invention can be more effectively exhibited. When the compression recovery rate of the resin particles after the weather resistance test under 20% compression deformation is the upper limit or less, even when a flexible substrate such as a PET film is used in the production of the light-control laminate, scratches on the surface of the substrate can be suppressed, and the visibility of the obtained light-control laminate can be improved.

[0042] Furthermore, the compression recovery rate of the resin particles when compressed by 10% (the compression recovery rate of the resin particles when compressed by 10%) is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, even more preferably 80% or more, particularly preferably more than 80%, most preferably 81% or more, and preferably 99% or less, more preferably 98% or less, and even more preferably 95% or less. When the compression recovery rate of the resin particles when compressed by 10% is equal to or greater than the lower limit, the gap between the substrates can be controlled with high precision, and the initial display unevenness of the resulting light-controlling laminate can be suppressed. When the compression recovery rate of the resin particles when compressed by 10% is equal to or less than the upper limit, even when a flexible substrate such as a PET film is used in the production of the light-controlling laminate, scratches on the surface of the substrate can be suppressed, and the visibility of the resulting light-controlling laminate can be improved. The compression recovery rate of the resin particles when compressed by 10% can be measured in the same manner as the compression recovery rate of the resin particles when compressed by 20% before the weather resistance test, except for changing the amount of compression deformation. The compression recovery rate of the resin particles after 10% compressive deformation is the compression recovery rate of the resin particles after 10% compressive deformation before the weather resistance test.

[0043] Methods for adjusting the compression recovery rate of the resin particles at 20% compressive deformation before the weather resistance test, the compression recovery rate of the resin particles at 20% compressive deformation after the weather resistance test, and the ratio (compression recovery rate of the resin particles at 20% compressive deformation after the weather resistance test / compression recovery rate of the resin particles at 20% compressive deformation before the weather resistance test) within preferred ranges include the following methods: A method using a preferred polymerizable component as the material for the resin particles, which will be described later; A method using a preferred material for the colorant, which will be described later; A method adjusting the particle size of the colorant, which will be described later; A method adjusting the content of the colorant, which will be described later; A method adjusting the thickness of the coating layer, which will be described later.

[0044] The 20% compressive elastic modulus of the resin particles is preferably 1 N / mm ２ More preferably, 200 N / mm ２ More preferably, 300 N / mm ２ or more, preferably 5000 N / mm ２or less, more preferably 4000 N / mm ２ More preferably, 3000 N / mm ２ Below, particularly preferably 1500 N / mm ２ Below 800 N / mm, most preferably ２ or less. When the 20% compressive elastic modulus of the 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 greater precision, and damage to the substrates can be prevented. Furthermore, when the 20% compressive elastic modulus of the resin particles is equal to or greater than the lower limit and equal to or less than the upper limit, breakage of the resin particles can be suppressed, thereby suppressing outflow of the colorant in the resin particles and preventing the occurrence of short circuits. As a result, the electrical conductivity reliability of the resulting light-controlling laminate can be improved.

[0045] The 20% compressive modulus of the resin particles can be measured, for example, as follows. Using a microcompression tester, the 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% compressive modulus of the resin particles can be calculated using the following formula. This measurement is performed on five resin particles, and the average value of the five measured values ​​is taken as the 20% compressive modulus. As the microcompression tester, for example, the "Fisherscope H-100" manufactured by Fischer and the "ENT-NEXUS" manufactured by Elionix can be used.

[0046] 20% compression elastic modulus (N / mm ２ ) = (3 / 2 １／２ ) F.S. －３／２ ・R －１／２ F: Load value (N) when resin particle is compressed and deformed by 20%; S: Compression displacement (mm) when resin particle is compressed and deformed by 20%; R: Radius of resin particle (mm)

[0047] The dielectric strength of the resin particles is preferably 5 kV / mm or more, more preferably 10 kV / mm or more, and even more preferably 15 kV / mm or more. When the dielectric strength of the resin particles is equal to or greater than the lower limit, the occurrence of short circuits can be suppressed, and the electrical conductivity reliability of the resulting light-control laminate can be improved. The upper limit of the dielectric strength of the resin particles is not particularly limited. The dielectric strength of the resin particles may be 70 kV / mm or less, 60 kV / mm or less, or 50 kV / mm or less. The range of the dielectric strength of the resin particles can be set by appropriately selecting the lower limit and the upper limit.

[0048] The dielectric strength of the resin particles can be measured, for example, as follows. 5 parts by weight of resin particles and 95 parts by weight of acrylic resin are mixed, and the resulting mixture is cured at 100°C for 6 hours to produce a resin film (size: 2 cm x 2 cm, thickness: particle diameter of resin particles). The dielectric strength of the resulting resin film is measured in insulating oil at 25°C using a dielectric breakdown tester (HAR series manufactured by Matsusada Precision Co., Ltd.) in accordance with JIS C2110-1:2016, and this is the dielectric strength of the resin particles.

[0049] Methods for adjusting the dielectric strength of the resin particles to a preferred range include using a material that is preferred for the colorant described below, adjusting the particle size of the colorant described below, and adjusting the content of the colorant described below.

[0050] The sphericity of the resin particles when sandwiched between two substrates at a pressure of 0.1 MPa is preferably 0.55 or more, more preferably 0.60 or more, even more preferably 0.70 or more, and preferably 1.0 or less, more preferably 0.99 or less, even more preferably 0.98 or less, and particularly preferably 0.95 or less. When the sphericity of the resin particles when sandwiched between two substrates at a pressure of 0.1 MPa is equal to or greater than the lower limit, the gap between the substrates can be controlled with even greater precision, and the occurrence of display unevenness in the resulting light-controlling laminate can be further suppressed. When the sphericity of the resin particles when sandwiched between two substrates at a pressure of 0.1 MPa is equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited.

[0051] The sphericity of resin particles sandwiched between two substrates at a pressure of 0.1 MPa can be measured, for example, as follows: A first substrate and a second substrate are prepared. Resin particles are sprayed onto the surface of the first substrate. A second substrate is placed on the surface opposite the sprayed resin particles from the first substrate side. A sealant (sealant) is applied to the edge of the surface of the second substrate facing the first substrate, and the resin particles are compressed from the surface of the second substrate opposite the resin particle side at a temperature of 90°C and a pressure of 0.1 MPa for 5 hours to produce a laminate comprising the first substrate, the second substrate, and resin particles disposed between the first substrate and the second substrate. The laminate is cut using an FIB, and the cross section is observed using a field emission scanning electron microscope (FE-SEM). The sphericity of the resin particles is measured by analyzing the obtained image. The sphericity of the resin particles can also be measured by taking an image of the prepared laminate by a method such as three-dimensional scanning and analyzing it with a computer or the like. When three-dimensional scanning or the like is not possible, the circularity can be measured by analyzing an image of the image taken by a method such as two-dimensional scanning with a computer or the like. The substrate may be the first substrate and the second substrate of the light-control laminate described below. The substrate is preferably a resin film, and more preferably a polyethylene terephthalate (PET) film. When a PET film is used to measure the sphericity, for example, a PET film ("ELECRYSTA" manufactured by Nitto Denko Corporation) or the like is used.

[0052] Methods for adjusting the sphericity of the resin particles when sandwiched between two substrates at the above-mentioned pressure of 0.1 MPa to within a preferred range include using a preferred polymerizable component as the material for the resin particles, as described below, and adjusting the thickness of the coating layer, as described below.

[0053] The static angle of repose of the resin particles is preferably 2° or more, more preferably 5° or more, even more preferably 7° or more, particularly preferably 10° or more, and is preferably 65° or less, more preferably 60° or less, and even more preferably 55° or less. When the static angle of repose of the resin particles is the lower limit or more, the handleability of the resin particles can be improved. When the static angle of repose of the resin particles is the upper limit or less, unintended aggregation of the resin particles can be prevented, and the handleability of the resin particles can be improved.

[0054] The static angle of repose of the resin particles can be measured, for example, as follows: 5 g of resin particles are dropped from a glass powder funnel (diameter 50 mm, foot diameter 15 mm) fixed at a height of 10 cm at 25° C., and after leaving it to stand for 60 seconds, the angle of the bottom of the pile of powder is measured with a protractor, and this angle is taken as the static angle of repose of the resin particles.

[0055] Methods for adjusting the static angle of repose of the resin particles to a preferred range include adjusting the thickness of the coating layer described below, forming irregularities on the surface of the resin particles (particularly the coating layer described below), and using a preferred polymerizable component as the material for the resin particles described below.

[0056] From the viewpoints of improving practicality, appropriately controlling the transmittance of the light-controlling laminate, and effectively suppressing light leakage, the particle diameter of the resin particles is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 10 μm or more, and is preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less.

[0057] The particle size of the resin particles is preferably an average particle size, and more preferably a number average particle size. The particle size of the resin particles can be determined, for example, by observing 50 random resin particles with an electron microscope or optical microscope and calculating the average particle size of each resin particle, or by performing laser diffraction particle size distribution measurement. In observation with an electron microscope or optical microscope, the particle size of each resin particle is determined as the particle size in equivalent circle diameter. In observation with an electron microscope or optical microscope, the average particle size of 50 random resin particles in equivalent circle diameter is approximately equal to the average particle size in equivalent sphere diameter. In laser diffraction particle size distribution measurement, the particle size of each resin particle is determined as the particle size in equivalent sphere diameter. The particle size of the resin particles is preferably calculated by laser diffraction particle size distribution measurement.

[0058] From the viewpoint of controlling the gap between the substrates with even higher precision, it is preferable that the resin particles do not contain resin particles having a particle diameter of 1.5 times or more the average particle diameter, or contain resin particles having a particle diameter of 1.5 times or more 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 resin particles having a particle diameter of 1.5 times or more the average particle diameter is preferably 1000 ppm or less, more preferably 100 ppm or less, even more preferably 10 ppm or less, and particularly preferably 0.1 ppm or less. From the viewpoint of controlling the gap between the substrates with even higher precision, it is most preferable that the content of resin particles having a particle diameter of 1.5 times or more the average particle diameter is 0 ppm (not contained).

[0059] The content (ppm) of resin particles having a particle size 1.5 times or more the average particle size can be measured as follows: Resin particles are filtered through a filter with a pore size 1.5 times the average particle size, the resin particles remaining on the filter are observed under an optical microscope, and the resin particles having a particle size 1.5 times or more the average particle size are counted. The number of counted resin particles is divided by the total number of filtered resin particles to calculate the content (ppm) of resin particles having a particle size 1.5 times or more the average particle size.

[0060] From the viewpoint of controlling the gap between the substrates with even greater precision, the CV value of the particle diameter of the resin particles is preferably 1.0% or more, more preferably 2.0% or more, and is preferably 10% or less, more preferably 8.0% or less.

[0061] The CV value (coefficient of variation) of the particle diameter of the resin particles can be measured as follows.

[0062] CV value (%) = (ρ / Dn) × 100, where ρ is the standard deviation of the particle diameter of the resin particles, and Dn is the average particle diameter of the resin particles.

[0063] From the viewpoint of controlling the gap between the substrates with even higher precision, the aspect ratio of the resin particles is preferably 1.5 or less, more preferably 1.3 or less. There is no particular limitation on the lower limit of the aspect ratio of the resin particles. The aspect ratio of the resin particles may be 1.0 or more, or may be 1.1 or more. The aspect ratio represents the major axis / minor axis ratio. The aspect ratio is preferably determined by observing 10 arbitrary resin particles with an electron microscope or an optical microscope, defining 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 ratio of each spherical resin particle.

[0064] From the viewpoint of improving the dispersibility of the resin particles in the photochromic layer of the obtained photochromic laminate, the specific gravity of the resin particles is preferably 1.0 or more, preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less.

[0065] From the viewpoint of effectively suppressing light leakage, the visible light transmittance of the resin particles is preferably 40% or less, more preferably 20% or less, and even more preferably 10% or less. The lower limit of the visible light transmittance of the resin particles is not particularly limited. The visible light transmittance of the resin particles may be 0.01% or more, 0.1% or more, or 1% or more.

[0066] The visible light transmittance of the resin particles can be measured as follows: A plate-shaped sample having the same composition as the resin particles is prepared, and spectroscopic measurement or the like is performed to measure the visible light transmittance in accordance with ISO 13837: 2008. Alternatively, the visible light transmittance can be measured by a method in accordance with JIS K6714 or the like.

[0067] The resin particles may or may not have irregularities on the surface of the resin particles. From the viewpoint of suppressing the tackiness of the resin particles, preventing unintended aggregation of the resin particles, and improving the handleability of the resin particles, it is preferable that the resin particles have irregularities on the surface of the resin particles. That is, it is preferable that the resin particles are resin particles having irregularities on the surface.

[0068] From the viewpoint of preventing unintended aggregation of the resin particles and improving the handleability of the resin particles, the height of the irregularities on the surface of the resin particles is preferably 20 nm or more, more preferably 30 nm or more, and preferably 1000 nm or less, more preferably 800 nm or less. The difference between the highest and lowest points on the surface of the resin particles is defined as the height of the irregularities on the surface of the resin particles.

[0069] Methods for forming irregularities on the surface of the resin particles include a method of adsorbing fine nanoparticles onto the surface of the resin particles, a method of polymerizing a resin particle material containing a polymerizable component in the presence of a non-polymerizable component and then removing the non-polymerizable component, and a method of adding fine nanoparticles to the resin particle material.

[0070] The resin particles according to the present invention are preferably used as spacers. The resin particles according to the present invention are particularly preferably used as spacers in a light-controlling laminate. The resin particles may be used as spacers for light-controlling glass or spacers for light-controlling films. The resin particles are preferably used as spacers for light-controlling glass or spacers for light-controlling films.

[0071] Each component of the resin particles will be described in detail below.

[0072] <Resin> The resin particles contain a resin. The resin particles preferably contain a polymer. The polymer is obtained by polymerizing a polymerizable component. The material of the resin particles contains a polymerizable component. The resin particles preferably contain a component derived from the polymerizable component. The resin particles preferably contain a polymer of the polymerizable component.

[0073] Examples of resins 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, phenolic resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamide-imide, polyether ether ketone, polyether sulfone, and divinylbenzene polymer. The divinylbenzene polymer may be a divinylbenzene copolymer. Examples of the divinylbenzene copolymer include a divinylbenzene-styrene copolymer and a divinylbenzene-(meth)acrylic acid ester copolymer. Since the compression characteristics 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 (polymerizable components) having an ethylenically unsaturated group.

[0074] When the resin particles are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group may be a non-crosslinkable monomer or a crosslinkable monomer.

[0075] 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, and cetyl (meth)acrylate. alkyl (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; oxygen atom-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, linearene, ethylene, and propylene; and conjugated diene compounds such as isoprene and butadiene.

[0076] Examples of the crosslinkable monomer include vinyl compounds such as vinyl monomers like divinylbenzene, 1,4-divinyloxybutane, and divinylsulfone; (meth)acrylic compounds such as polyfunctional (meth)acrylate compounds like tetramethylolmethane tetra(meth)acrylate, 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; and allyl compounds such as trimethylolmethane di(meth)acrylate. silane 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 suitable silane alkoxides include 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-ends silicone oil, and side-chain silicone oil; and carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride.

[0077] The resin particles can be obtained by polymerizing the polymerizable monomer having an ethylenically unsaturated group. The polymerization method is not particularly limited. The polymerizable monomer having an ethylenically unsaturated group may be polymerized by a known method such as radical polymerization, ionic polymerization, polycondensation (condensation polymerization, polycondensation), addition condensation, living polymerization, or living radical polymerization.

[0078] The resin particles can be easily obtained by radical polymerization using the polymerizable monomer having an ethylenically unsaturated group, for example, by a suspension polymerization method in the presence of a radical polymerization initiator, or a seed polymerization method or a dispersion polymerization method in which a monomer is swelled and polymerized together with a radical polymerization initiator using non-crosslinked seed particles.

[0079] From the viewpoint of controlling the gap between the substrates with higher precision, the polymerizable component and the material of the resin particles preferably contain a polyfunctional (meth)acrylate compound, i.e., from the viewpoint of controlling the gap between the substrates with higher precision, the resin particles preferably contain a component derived from a polyfunctional (meth)acrylate compound.

[0080] The polyfunctional (meth)acrylate compound may be a difunctional or higher (meth)acrylate compound, a trifunctional or higher (meth)acrylate compound, a tetrafunctional or higher (meth)acrylate compound, or a 10- or lower functional (meth)acrylate compound. The polyfunctional (meth)acrylate compound may be used alone or in combination of two or more. The polyfunctional (meth)acrylate compound is preferably polytetramethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, or dipentaerythritol tetra(meth)acrylate.

[0081] In 100% by weight of the resin particles, the content of the resin (polymer of polymerizable component) 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 resin (polymer of polymerizable component) is above the lower limit and below the upper limit, the compression recovery rate of the resin particles at 20% compressive deformation before and after the weather resistance test and the 20% compressive modulus of the resin particles can be adjusted within a preferred range, and the gap between substrates can be controlled with even greater precision. In particular, from the viewpoint of appropriately lowering the 20% compressive modulus of the resin particles, it is preferable that the resin particles contain a component derived from a polyfunctional (meth)acrylate compound. From the viewpoint of effectively reducing the 20% compressive modulus of the resin particles, the content of the component derived from the polyfunctional (meth)acrylate compound in 100% by weight of the resin particles is preferably 50% by weight or more, more preferably 70% by weight or more, and preferably 100% by weight or less. From the viewpoint of further effectively reducing the 20% compressive modulus of the resin particles, it is more preferable that the polyfunctional (meth)acrylate compound contains polytetramethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, or dipentaerythritol tetra(meth)acrylate. Furthermore, from the viewpoint of moderately increasing the 20% compressive modulus of the resin particles, it is preferable that the resin particles contain a component derived from divinylbenzene. From the viewpoint of effectively increasing the 20% compressive modulus of the resin particles, the content of the component derived from divinylbenzene in 100% by weight of the resin particles is preferably 5% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less.

[0082] The content of the polymerizable component in 100% by weight of the resin particle material 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 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 polymerizable component is above the lower limit and below the upper limit, the compression recovery rate of the resin particles at 20% compression deformation before and after the weather resistance test and the 20% compressive modulus of the resin particles can be adjusted within preferred ranges, thereby enabling more precise control of the gap between substrates. In particular, from the viewpoint of appropriately lowering the 20% compressive modulus of the resin particles, it is preferable that the resin particle material contains a polyfunctional (meth)acrylate compound. From the viewpoint of effectively lowering the 20% compressive modulus of the resin particles, the content of the polyfunctional (meth)acrylate compound in 100% by weight of the resin particle material is preferably 50% by weight or more, more preferably 70% by weight or more, and preferably 100% by weight or less. From the viewpoint of more effectively reducing the 20% compressive modulus of the resin particles, it is more preferable that the polyfunctional (meth)acrylate compound contains polytetramethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, or dipentaerythritol tetra(meth)acrylate. Furthermore, from the viewpoint of moderately increasing the 20% compressive modulus of the resin particles, it is preferable that the material of the resin particles contains divinylbenzene. From the viewpoint of effectively increasing the 20% compressive modulus of the resin particles, the content of divinylbenzene in 100% by weight of the material of the resin particles is preferably 5% by weight or more, preferably 50% by weight or less, more preferably 30% by weight or less.

[0083] <Colorant> From the viewpoint of effectively suppressing light leakage, the resin particles (and the material of the resin particles) preferably 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 conduction 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. When the resin particles include a substrate particle and a coating layer described below, the substrate particle (and the material of the substrate particle) may contain a colorant, the coating layer (and the material of the coating layer) may contain a colorant, or the substrate particle and the coating layer may contain a colorant. When the resin particles include a substrate particle and a coating layer described below, the substrate particle or the coating layer preferably contains a colorant. When the resin particles include a substrate particle and a coating layer described below, from the viewpoint of protecting the substrate particle from damage due to light and further improving the weather resistance of the resin particles, the coating layer preferably contains a colorant.

[0084] Examples of the colorant include inorganic particles, dyes, pigments, etc. The colorant may be used alone or in combination of two or more kinds.

[0085] Examples of the inorganic particles include carbon black, carbon nanotubes, titanium black, graphene, iron oxide, zinc oxide, calcium carbonate, alumina, kaolin clay, calcium silicate, magnesium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, talc, feldspar powder, mica, baryte, barium carbonate, titanium oxide, manganese oxide, and glass beads. The inorganic particles are preferably carbon black, titanium black, or manganese oxide.

[0086] Examples of the dye include pyrene-based dyes, aminoketone-based dyes, anthraquinone-based dyes, and azo-based dyes.

[0087] Examples of the pyrene dye include Solvent Green 5 (CAS 79869-59-3) and Solvent Green 7 (CAS 6358-69-6).

[0088] Examples of the aminoketone dyes include Solvent Yellow 98 (CAS 12671-74-8), Solvent Yellow 85 (CAS 12271-01-1), Solvent Red 179 (CAS 8910-94-5), and Solvent Red 135 (CAS 71902-17-5).

[0089] Examples of the anthraquinone dyes include Solvent Yellow 163 (CAS 13676091-0), Solvent Red 207 (CAS 15958-69-6), Disperse Red 92 (CAS 12236-11-2), Solvent Violet 13 (CAS 81-48-1), Disperse Violet 31 (CAS 6408-72-6), Solvent Blue 97 (CAS 61969-44-6), Solvent Blue 45 (CAS 37229-23-5), Solvent Blue 104 (CAS 116-75-6), and Disperse Red 92 (CAS 12236-11-2). Blue 214 (CAS 104491-84-1) and the like.

[0090] 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).

[0091] The dye may be an organic dye or an inorganic dye. The dye may be a red dye, a blue dye, a yellow dye, or a black dye. The dye may be a polymerizable dye or a non-polymerizable dye. Only one type of the dye may be used, or two or more types may be used in combination.

[0092] From the viewpoints of effectively suppressing light leakage, effectively suppressing discoloration, and further increasing the electrical reliability of the resulting photochromic laminate, the dye is preferably an organic dye, more preferably a black dye, and even more preferably an organic black dye. From the viewpoint of preventing contamination of the photochromic layer of the resulting photochromic laminate, the dye is preferably a polymerizable dye, more preferably a polymerizable black dye.

[0093] The pigment may be an organic pigment or an inorganic pigment. The organic pigment may or may not contain 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.

[0094] From the viewpoint of effectively suppressing light leakage, effectively suppressing discoloration, and further increasing the electrical reliability of the resulting light-controlling laminate, the pigment is more preferably an organic pigment, more preferably a black pigment, and even more preferably an organic black pigment.

[0095] Examples of the organic black pigments 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.

[0096] The colorant preferably contains carbon black, titanium black, manganese oxide, a pigment, or a dye, and more preferably contains carbon black, titanium black, manganese oxide, an organic black pigment, or an organic black dye. The colorant more preferably contains a pigment, even more preferably contains an organic black pigment, and particularly preferably contains an azo pigment or a perylene pigment. In these cases, light leakage can be effectively suppressed, discoloration can be effectively suppressed, and the electrical reliability of the resulting light-control laminate can be further improved. Furthermore, from the viewpoints of effectively improving the dielectric strength, further suppressing the occurrence of short circuits, and further improving the electrical reliability of the resulting light-control laminate, the colorant preferably contains titanium black, manganese oxide, an organic black pigment, or an organic black dye.

[0097] The particle diameter of the colorant is preferably 10 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and preferably 700 nm or less, more preferably 600 nm or less, even more preferably 500 nm or less, even more preferably 450 nm or less, particularly preferably 400 nm or less, and most preferably 380 nm or less. When the particle diameter of the colorant is above the lower limit, leakage of the colorant from the resin particles can be suppressed, preventing contamination of the light-controlling layer of the obtained light-controlling laminate. When the particle diameter of the colorant is below the upper limit, the light absorption efficiency of the colorant is improved, and the resin particles can be protected from damage by light, thereby further improving the weather resistance of the resin particles.

[0098] The particle diameter of the colorant is preferably an average particle diameter. When the colorant contains two or more colorants, the average particle diameter of the entire colorant is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, and is preferably 700 nm or less, more preferably 600 nm or less, even more preferably 500 nm or less, even more preferably 450 nm or less, particularly preferably 400 nm or less, and most preferably 380 nm or less. The average particle diameter indicates the weight-average particle diameter. The average particle diameter can be measured, for example, by dynamic light scattering using a light scattering measurement device with a laser as a light source. An example of the light scattering measurement device is the "DLS-6000AL" manufactured by Otsuka Electronics Co., Ltd.

[0099] Methods for adjusting the particle size of the colorant to fall within the preferred range include a method using a homogenizer, a method using a ball mill, and a method using shear force during wet dispersion.

[0100] The content of the colorant in 100% by weight of the resin particles is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, even more preferably 3.0% by weight or more, and 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 greater 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 insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the resin particles contain two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0101] The content (wt %) of the colorant contained in the resin particles can be measured, for example, by the following method: 1 g of resin particles is weighed, and the resin particles are baked at 350°C for 1 hour in an electric furnace ("ROP-001P" manufactured by AS ONE Corporation), and the residue is weighed and used as the colorant content.

[0102] The content of the colorant relative to 100 parts by weight of the resin (polymer of polymerizable component) in the resin particles is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less. When the content of the colorant is equal to or greater 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 insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the resin particles contain two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0103] In the resin particle material, the content of the colorant is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, relative to 100 parts by weight of the polymerizable component. When the content of the colorant is equal to or greater 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 insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the resulting light-control laminate can be further improved. When the resin particles contain two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0104] The content of the colorant in 100% by weight of the base particles is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, even more preferably 3.0% by weight or more, and 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 greater 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 insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the base particles contain two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0105] The content of the colorant relative to 100 parts by weight of the resin (polymer of polymerizable component) in the base particle is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less. When the content of the colorant is above the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is below the upper limit, the insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the base particle contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0106] In the material of the base particle, the content of the colorant relative to 100 parts by weight of the polymerizable component is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less. When the content of the colorant is above the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is below the upper limit, the insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the base particle contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0107] The content of the colorant in 100% by weight of the coating layer is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, even more preferably 3.0% by weight or more, even more preferably 8.0% by weight or more, even more preferably 10% by weight or more, particularly preferably 20% by weight or more, most preferably 25% by weight or more, and preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 40% by weight or less. When the content of the colorant is above the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is below the upper limit, the insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the coating layer contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0108] The content of the colorant relative to 100 parts by weight of the resin (polymer of polymerizable component) in the coating layer is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, even more preferably 8.0 parts by weight or more, even more preferably 12 parts by weight or more, particularly preferably 25 parts by weight or more, most preferably 35 parts by weight or more, and preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 40 parts by weight or less. When the content of the colorant is above the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is below the upper limit, the insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-controlling laminate can be further improved. When the coating layer contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0109] In the material for the coating layer, the content of the colorant relative to 100 parts by weight of the polymerizable component is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, even more preferably 8.0 parts by weight or more, even more preferably 12 parts by weight or more, particularly preferably 25 parts by weight or more, most preferably 35 parts by weight or more, and preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 40 parts by weight or less. When the content of the colorant is above the lower limit, light leakage can be more effectively suppressed. When the content of the colorant is below the upper limit, the insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the resulting light-control laminate can be further improved. When the coating layer contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0110] <Other Components> The 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.

[0111] Next, specific embodiments of the present invention will be described with reference to the drawings.

[0112] FIG. 1 is a cross-sectional view schematically showing a resin particle according to a first embodiment of the present invention.

[0113] Resin particle 1 does not have a coating layer on the surface of resin particle 1. Resin particle 1 does not have a base particle and a coating layer disposed on the surface of the base particle.

[0114] Resin particles 1 were exposed to light using a sunshine carbon arc lamp at 85°C, 50% RH, and an illuminance of 255 W / m ２ When a weather resistance test is conducted under the conditions of 1000 to 500 hours, the ratio of the compression recovery rate of the resin particles after the weather resistance test to the compression recovery rate of the resin particles before the weather resistance test is 0.50 or more.

[0115] FIG. 2 is a cross-sectional view schematically showing a resin particle according to a second embodiment of the present invention.

[0116] The resin particle 1A includes a base particle 2A and a coating layer 3A disposed on the surface of the base particle 2A.

[0117] FIG. 3 is a cross-sectional view schematically showing a resin particle according to a third embodiment of the present invention.

[0118] Resin particle 1B includes base particle 2B and coating layer 3B disposed on the surface of base particle 2B. Resin particle 1B has irregularities on the surface of resin particle 1B (coating layer 3B).

[0119] (Base particle) The resin particle may or may not have a base particle and a coating layer disposed on the surface of the base particle. From the viewpoint of protecting the center portion of the resin particle from damage by light and further improving the weather resistance of the resin particle, the resin particle preferably has a base particle and a coating layer disposed on the surface of the base particle.

[0120] The base particle preferably contains a resin. The base particle preferably contains a polymer. The polymer is obtained by polymerizing a polymerizable component. The base particle preferably contains a component derived from the polymerizable component. The base particle preferably contains a polymer of the polymerizable component.

[0121] Examples of the resin in the base particle include the resins described above.

[0122] The base particles may contain a colorant or may not contain a colorant. From the viewpoint of improving the display contrast of the obtained light-control laminate, the base particles preferably contain a colorant, and more preferably contain a resin and a colorant.

[0123] Examples of the colorant in the base particles include the colorants described above.

[0124] The colorant in the base particles preferably contains carbon black, titanium black, manganese oxide, a pigment, or a dye, and more preferably contains carbon black, titanium black, manganese oxide, an organic black pigment, or an organic black dye. The colorant in the base particles more preferably contains a pigment, even more preferably contains an organic black pigment, and particularly preferably contains an azo pigment or a perylene pigment. In these cases, light leakage can be effectively suppressed, discoloration can be effectively suppressed, and the electrical conductivity reliability of the resulting light-control laminate can be further improved.

[0125] The particle diameter of the colorant in the base particle is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, and is preferably 700 nm or less, more preferably 600 nm or less, and even more preferably 500 nm or less. When the particle diameter of the colorant in the base particle is equal to or more than the above lower limit and equal to or less than the above upper limit, the effects of the present invention can be more effectively exhibited.

[0126] The particle diameter of the colorant in the base particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the colorant in the base particles can be measured, for example, as follows. Fifty arbitrary resin particles are cut out from the cross section of the resin particles using an FIB and a microtome, etc. Then, the cross section is observed using a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM), and the particle diameters of the colorant in the base particles in the resin particles are measured, and the arithmetic average of these is taken as the particle diameter of the colorant in the base particles.

[0127] From the viewpoint of effectively suppressing light leakage, the particle diameter of the base 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.

[0128] The particle diameter of the base particles is preferably an average particle diameter, and more preferably a number average particle diameter. The particle diameter of the base particles is determined, for example, by observing 50 random base particles with an electron microscope or optical microscope and calculating the average value. When observed with an electron microscope or optical microscope, the particle diameter of each base particle is determined as the particle diameter in equivalent circle diameter. When observed with an electron microscope or optical microscope, the average particle diameter in equivalent circle diameter of 50 random base particles is approximately equal to the average particle diameter in equivalent sphere diameter. When using a particle size distribution measuring device, the particle diameter of each base particle is determined as the particle diameter in equivalent sphere diameter. The particle diameter of the base particles is preferably calculated using a particle size distribution measuring device. When measuring the particle diameter of the base particles in resin particles, it can be measured, for example, as follows.

[0129] The resin particles were added to Kulzer's Technovit 4000 so that the content was 30% by weight, and dispersed to prepare an embedded resin body for substrate particle inspection. An ion milling device (Hitachi High-Technologies Corporation's IM4000) was used to cut out a cross section of the resin particle so that it passed through the center of the substrate particles dispersed in the embedded resin body. Then, using a field emission scanning electron microscope (FE-SEM) with an image magnification set to 25,000x, 50 resin particles were randomly selected and the substrate particles of each resin particle were observed. The particle diameter of the substrate particles in each resin particle was measured, and the arithmetic average was used to determine the particle diameter of the substrate particles.

[0130] The content of the colorant in 100% by weight of the base particles is preferably 0.5% by weight or more, more preferably 1.0% by weight or more, even more preferably 3.0% by weight or more, and 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 greater 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 insulating reliability of the resin particles can be improved, and as a result, the conductive reliability of the obtained light-control laminate can be further improved. When the resin particles contain two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0131] The content of the polymerizable component in 100% by weight of the material of the base particle 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 polymerizable component is equal to or more than the lower limit and equal to or less than the upper limit, the gap between the base materials can be controlled with even higher precision.

[0132] In the material of the base particle, the content of the colorant is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, relative to 100 parts by weight of the polymerizable component. When the content of the colorant is equal to or greater than the lower limit, the light-blocking properties of the base particle can be further improved. When the content of the colorant is equal to or less than the upper limit, the specific gravity of the resin particles can be adjusted within a preferred range, and the dispersibility of the resin particles in the light-control layer of the obtained light-control laminate can be improved. When the base particle contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0133] (Coating Layer) The coating layer preferably contains a resin or inorganic particles.

[0134] The resin in the coating layer may be any of the resins described above, etc. The resin may be an adhesive resin.

[0135] Examples of the inorganic particles include silica (silicon dioxide), titania (titanium dioxide), and alumina (aluminum oxide). The inorganic particles preferably contain silica.

[0136] From the viewpoint of improving the dispersibility of the resin particles in the photochromic layer of the obtained photochromic laminate, the material of the coating layer (and the coating layer) preferably contains a compound having an aromatic skeleton. From the viewpoint of improving the dispersibility of the resin particles in the photochromic layer of the obtained photochromic laminate, the material of the coating layer preferably contains a compound having an aromatic skeleton, and more preferably contains divinylbenzene or styrene.

[0137] From the viewpoint of enhancing the anchoring effect on flexible substrates such as PET films in the production of a light-controlling laminate, the material of the coating layer (and the coating layer) preferably contains a compound having a hydrocarbon group with 3 or more carbon atoms in its main chain (a compound in which the hydrocarbon group has 3 or more carbon atoms in its main chain). From the viewpoint of enhancing the anchoring effect on flexible substrates such as PET films in the production of a light-controlling laminate, the number of carbon atoms in the main chain of the hydrocarbon group is preferably 3 or more, more preferably 5 or more, and preferably 35 or less, more preferably 30 or less.

[0138] From the viewpoint of forming irregularities on the surface of the resin particles and preventing unintended aggregation of the resin particles, it is preferable that the material of the coating layer (and the coating layer) contains silicon atoms. The silicon atoms may be used alone or in the form of a compound. Examples of compounds containing silicon atoms include silica (silicon dioxide), silicon carbide, and silicone compounds.

[0139] From the viewpoint of protecting the resin particles (particularly the base particles) from damage caused by light and further enhancing the weather resistance of the resin particles, it is preferable that the material of the coating layer (and the coating layer) contains a compound having an aromatic skeleton, a compound having a hydrocarbon group with three or more carbon atoms in the main chain, or a silicon atom.

[0140] The coating layer (and the material of the coating layer) may or may not contain a colorant. From the viewpoint of protecting the resin particles (particularly, the base particles) from damage due to light and further improving the weather resistance of the resin particles, it is preferable that the coating layer (and the material of the coating layer) contain a colorant.

[0141] Examples of the colorant in the coating layer include the colorants described above.

[0142] The colorant in the coating layer preferably contains carbon black, titanium black, manganese oxide, a pigment, or a dye, and more preferably contains carbon black, titanium black, manganese oxide, an organic black pigment, or an organic black dye. The colorant in the coating layer more preferably contains a pigment, even more preferably contains an organic black pigment, and particularly preferably contains an azo pigment or a perylene pigment. In these cases, light leakage can be effectively suppressed, discoloration can be effectively suppressed, and the electrical conductivity reliability of the resulting light-control laminate can be further improved.

[0143] The particle diameter of the colorant in the coating layer is preferably 10 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and preferably 700 nm or less, more preferably 600 nm or less, even more preferably 500 nm or less. When the particle diameter of the colorant in the coating layer is equal to or greater than the lower limit, leakage of the colorant from the resin particles can be suppressed, and contamination of the photochromic layer of the resulting photochromic laminate can be prevented. When the particle diameter of the colorant in the coating layer is equal to or less than the upper limit, the effects of the present invention can be more effectively exhibited.

[0144] The particle size of the colorant in the coating layer is preferably an average particle size, more preferably a number average particle size, and can be measured in the same manner as the particle size of the colorant in the base particle.

[0145] The thickness of the coating layer is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 30 nm or more, even more preferably 100 nm or more, still more preferably 160 nm or more, particularly preferably 200 nm or more, and most preferably 220 nm or more, and is preferably 1000 nm or less, more preferably 800 nm or less, and even more preferably 500 nm or less. When the thickness of the coating layer is equal to or greater than the above lower limit and equal to or less than the above upper limit, unintended aggregation of the resin particles can be prevented, and the weather resistance of the resin particles can be further improved.

[0146] From the viewpoint of more effectively exerting the effects of the present invention, the area of ​​the portion covered by the coating layer (coverage rate by the coating layer) of the total surface area of ​​the base particle (100%) is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, and most preferably 100%. From the viewpoint of more effectively exerting the effects of the present invention, it is preferable that the coating layer covers the entire surface of the base particle. The coverage rate by the coating layer can be measured by the following method.

[0147] The resin particles are observed from one direction using a scanning electron microscope (SEM), and the coverage is calculated from the total area of ​​the coating layer within the circle at the outer periphery of the surface of the base particle in the observed image, as a percentage of the total area within the circle at the outer periphery of the surface of the base particle. The coverage by the coating layer is preferably calculated as an average coverage by observing 20 resin particles and averaging the measurement results for each resin particle.

[0148] In the material for the coating layer, the content of the colorant is preferably 0.5 parts by weight or more, more preferably 1.0 parts by weight or more, even more preferably 3.0 parts by weight or more, and preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and even more preferably 10 parts by weight or less, relative to 100 parts by weight of components other than the colorant. When the content of the colorant is equal to or greater than the lower limit, the light-blocking properties of the coating layer can be further improved. When the content of the colorant is equal to or less than the upper limit, the specific gravity of the resin particles can be adjusted to a preferred range, and the dispersibility of the resin particles in the light-control layer of the obtained light-control laminate can be improved. When the coating layer contains two or more colorants, the content of the colorant refers to the total content of the two or more colorants.

[0149] (Light-modulating laminate) The light-modulating laminate according to the present invention includes a first substrate, a second substrate, and a light-modulating layer disposed between the first substrate and the second substrate. In the light-modulating laminate according to the present invention, the light-modulating layer contains the resin particles.

[0150] The photochromic laminate according to the present invention has the above-described configuration, and therefore the gap between the substrates can be controlled with high precision, and the electrical conductivity reliability of the resulting photochromic laminate can be improved.

[0151] The light-control laminate may be a PDLC (Polymer Dispersed Liquid Crystal) type light-control laminate, a SPD (Suspended Particle Device) type light-control laminate, or a GHLC (Guest-Host Liquid Crystal) type light-control laminate. The light-control laminate is preferably a PDLC or GHLC type light-control laminate. The light-control laminate does not have to be a liquid crystal display device, and may be a light-control laminate different from a liquid crystal display device. The light-control laminate does not have to be a liquid crystal display element, and may be a light-control laminate different from a liquid crystal display element.

[0152] Fig. 4 is a cross-sectional view schematically showing a PDLC-type light-controlling laminate including resin particles according to a first embodiment of the present invention. Fig. 5 is a cross-sectional view schematically showing an SPD-type light-controlling laminate including resin particles according to a first embodiment of the present invention. Fig. 6 is a cross-sectional view schematically showing a GHLC-type light-controlling laminate including resin particles according to a first embodiment of the present invention. Note that in Figs. 4 to 6, the size, thickness, shape, and amount of addition of the light-controlling layer and resin particles have been appropriately modified from the actual size and shape for the sake of convenience of illustration.

[0153] The PDLC-type light-switching laminate 11 shown in Fig. 4 includes a first substrate 7, a second substrate 8, and a light-switching layer 4. The light-switching layer 4 is sandwiched between the first substrate 7 and the second substrate 8. The light-switching layer 4 is disposed between the first substrate 7 and the second substrate 8. A sealant may be disposed around the light-switching layer 4 between the first substrate 7 and the second substrate 8.

[0154] The light-controlling layer 4 includes 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 a capsule-like state in the binder 4B. The liquid crystal material may be dispersed in the binder in a capsule-like state, or the liquid crystal material may be dispersed in the binder as a continuous phase.

[0155] The resin particles 1 are in contact with the first substrate 7 and the second substrate 8. The resin particles 1 control the gap between the first substrate 7 and the second substrate 8.

[0156] Electrodes (not shown) are formed on the surfaces of the first substrate 7 and the second substrate 8. Examples of materials for the electrodes include indium tin oxide (ITO). The electrodes are preferably transparent electrodes.

[0157] 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 therefore, due to the difference in refractive index between the binder 4B and the liquid crystal material, the incident light is scattered in the binder 4B, resulting in an opaque state.

[0158] When an electric field is applied to the PDLC 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 equal, allowing light to pass through, resulting in a transparent state.

[0159] The SPD-type photochromic stack 21 shown in Fig. 5 includes a first substrate 7, a second substrate 8, and a photochromic layer 5. The photochromic layer 5 is sandwiched between the first substrate 7 and the second substrate 8. The photochromic layer 5 is disposed between the first substrate 7 and the second substrate 8.

[0160] The light control layer 5 includes 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.

[0161] 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.

[0162] The resin particles 1 are in contact with the first substrate 7 and the second substrate 8. The resin particles 1 control the gap between the first substrate 7 and the second substrate 8.

[0163] Electrodes (not shown) are formed on the surfaces of the first substrate 7 and the second substrate 8. Examples of materials for the electrodes include indium tin oxide (ITO). The electrodes are preferably transparent electrodes.

[0164] When no electric field is applied to the SPD-type dimming stack 21, the incident light is absorbed, scattered, or reflected by the light-controlling particles 5Ab due to Brownian motion of the light-controlling particles 5Ab dispersed in the dispersion medium 5Aa that constitutes the droplets 5A of the light-controlling suspension, and the incident light cannot pass through the dimming layer 5.

[0165] 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. As a result, incident light can pass between the aligned light control particles 5Ab and be transmitted through the light control layer 5.

[0166] The GHLC light switchable stack 31 shown in Fig. 6 includes a first substrate 7, a second substrate 8, and a light switchable layer 6. The light switchable layer 6 is sandwiched between the first substrate 7 and the second substrate 8. The light switchable layer 6 is disposed between the first substrate 7 and the second substrate 8. A sealant may be disposed around the light switchable layer 6 between the first substrate 7 and the second substrate 8. The GHLC light switchable stack 31 shown in Fig. 6 is a GHLC light switchable stack in a state where no electric field is applied.

[0167] The light-modulating layer 6 includes resin particles 1, liquid crystals 6A, and dichroic dyes 6B. The liquid crystals 6A are liquid crystal materials. To make it easier to visualize the orientation of the liquid crystal molecules in the liquid crystals 6A, oriented liquid crystals 6Aa are also shown. The oriented liquid crystals 6Aa are dispersed in the light-modulating layer 6. The liquid crystals 6A and the liquid crystal material may be dispersed in the form of capsules or as a continuous phase in the light-modulating layer 6. The dichroic dyes 6B have different light absorption levels depending on the axial direction. The dichroic dyes 6B are dispersed in the light-modulating layer 6. The dichroic dyes 6B are oriented along the orientation direction of the liquid crystals 6A (oriented liquid crystals 6Aa).

[0168] The resin particles 1 are in contact with the first substrate 7 and the second substrate 8. The resin particles 1 control the gap between the first substrate 7 and the second substrate 8.

[0169] Electrodes (not shown) are formed on the surfaces of the first substrate 7 and the second substrate 8. Examples of materials for the electrodes include indium tin oxide (ITO). The electrodes are preferably transparent electrodes.

[0170] When no electric field is applied to the GHLC type dimming stack 31, the liquid crystal molecules in the liquid crystal 6A (oriented liquid crystal 6Aa) are oriented in a direction perpendicular to the incident light, and the incident light is absorbed or scattered by the dichroic dye 6B, which is also oriented in the perpendicular direction, resulting in an opaque state.

[0171] When an electric field is applied to the GHLC-type light-control stack 31, the liquid crystal molecules in the liquid crystal 6A (oriented liquid crystal 6Aa) are aligned parallel to the electric field, and the dichroic dye 6B is also aligned parallel to the electric field, resulting in a transparent state.

[0172] <Light Control Layer> The light control layer preferably has a light control property. Light control property is a property in which the visible light transmittance changes depending on whether an electric field is applied or not, thereby enabling the amount of incident light to be adjusted. The light control layer contains the resin particles.

[0173] (PDLC System) The light-controlling layer preferably further contains a binder and a liquid crystal material dispersed in the binder.

[0174] The liquid crystal material is not particularly limited. The liquid crystal material has the property of changing its orientation when an electric field is applied. 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.

[0175] Examples of the nematic liquid crystal material include cyanobiphenyls, phenyl esters, azoxybenzenes, fluorine-containing biphenyls, carbonate esters, Schiff bases, etc. The nematic liquid crystal material may be used alone or in combination of two or more.

[0176] 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, cyclohexylcarboxylates, phenylcyclohexanes, biphenylcyclohexanes, pyrimidines, dioxanes, cyclohexylcyclohexane esters, cyclohexylethanes, cyclohexanes, tolanes, alkenyls, stilbenes, and condensed polycyclics, as well as materials obtained by adding a chiral component made of an optically active material such as a Schiff base, azo, ester, or biphenyl to a mixed liquid crystal of these. Only one type of cholesteric liquid crystal material may be used, or two or more types may be used in combination.

[0177] The binder holds the liquid crystal material and suppresses its flow. There are no particular limitations on the binder, as long as it is insoluble in the liquid crystal material, has strength sufficient to withstand external forces, and is highly transparent to reflected and incident light. Examples of binder materials 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, as well as materials that can be emulsified in water, such as fluororesins, 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.

[0178] The binder is preferably crosslinked by a crosslinking agent. The crosslinking agent is not particularly limited as long as it forms crosslinks between the binders and hardens, makes the binder less soluble, or insoluble. Examples of the crosslinking agent include acetaldehyde, glutaraldehyde, glyoxal, potassium alum hydrate, 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.

[0179] (SPD Method) The light control layer preferably further includes a resin matrix and a light control suspension dispersed in the resin matrix.

[0180] The light control suspension includes a dispersion medium and light control particles dispersed in the dispersion medium.

[0181] Examples of the light control particles include carbon 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 types.

[0182] The dispersion medium disperses the light control particles in a fluidizable state. The dispersion medium selectively adheres to and coats the light control particles, and acts to move the light control particles into the phase-separated droplet phase upon phase separation with the resin matrix. It is preferable that the dispersion medium be a material that is non-conductive and has no affinity with the resin matrix. Furthermore, the dispersion medium is preferably a liquid copolymer that, when formed into a light-control laminate, has a refractive index similar to that of the resin matrix. The liquid copolymer is preferably a (meth)acrylic acid ester oligomer having a fluoro group or a hydroxyl group, and more preferably a (meth)acrylic acid ester oligomer having a fluoro group and a hydroxyl group. When such a liquid copolymer is used, the monomer units with the fluoro group or hydroxyl group face the light control particles, and the remaining monomer units stabilize the droplets of the light control suspension within the resin matrix. This facilitates dispersion of the light control particles within the light control suspension, and the light control particles are easily guided into the droplets that phase-separate upon phase separation with the resin matrix.

[0183] 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 acrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, and 1H,1H,5H-octafluoropentyl acrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer. , 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.

[0184] 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 preferably 20,000 or less, more preferably 10,000 or less.

[0185] The light control layer can be produced using a resin material for forming the resin matrix and the light control suspension.

[0186] The resin material is preferably a resin material that is cured by irradiation with energy rays. Examples of resin materials that are cured by irradiation with energy rays include polymer compositions containing a photopolymerization initiator and a polymer compound that is cured by energy rays such as ultraviolet rays, visible light, and electron beams. Examples of the polymer compositions include polymer compositions containing a polymerizable monomer having an ethylenically unsaturated group and a photopolymerization initiator. Examples of the polymerizable monomer having an ethylenically unsaturated group include non-crosslinkable monomers and crosslinkable monomers.

[0187] The non-crosslinkable monomer may be the non-crosslinkable monomer described above. The crosslinkable monomer may be the crosslinkable monomer described above.

[0188] 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.

[0189] 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 promoter, and may also contain a solvent.

[0190] (GHLC System) The light-controlling layer preferably further contains a liquid crystal material and a dichroic dye.

[0191] The liquid crystal material may be the above-mentioned PDLC type liquid crystal material.

[0192] Examples of the dichroic dye include the above-mentioned azo dyes, azo pigments, anthraquinone dyes, anthraquinone pigments, dioxane dyes, dioxane pigments, etc. From the viewpoint of improving weather resistance and affinity with liquid crystal materials, the dichroic dye preferably includes an anthraquinone dye, an anthraquinone pigment, an azo dye, or an azo pigment.

[0193] <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 through the transparent substrate, the substance can be seen. Transparent also includes, for example, translucency. The transparent substrate may be colorless and transparent, or colored and transparent.

[0194] The materials of the first substrate and the second substrate are not particularly limited. The materials of the first substrate and the second substrate may be the same or different. Examples of materials for the first substrate and the second substrate include glass and resin films. Examples of the glass include soda-lime glass, lead glass, borosilicate glass, and glass of various compositions for general construction, as well as functional glass such as heat-reflecting glass, heat-absorbing glass, and tempered glass. Examples of the resin film include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, and acrylic resin films. Due to their excellent transparency, formability, adhesion, processability, etc., the first substrate and the second substrate are preferably resin substrates, more preferably resin films, and even more preferably polyethylene terephthalate (PET) films.

[0195] 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. The conductive film may be made of indium tin oxide (ITO), SnO ２ , and In２ O ３ The conductive film is preferably a transparent conductive film.

[0196] 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, more preferably 80% or more.

[0197] The visible light transmittance of the first substrate and the second substrate can be measured by spectroscopic measurement or the like in accordance with ISO 13837:2008.

[0198] 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.

[0199] The following materials were prepared:

[0200] (Polymerizable component) Polypropylene glycol diacrylate ("APG-400" manufactured by Shin-Nakamura Chemical Co., Ltd.) Divinylbenzene (a compound having an aromatic skeleton, "DVB960" manufactured by Nippon Steel Chemical Co., Ltd.) Isobornyl acrylate ("IBXA" manufactured by Shin-Nakamura Chemical Co., Ltd.) Cyclohexyl methacrylate ("CHMA" manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl methacrylate ("MMA" manufactured by Mitsubishi Rayon Co., Ltd.) Styrene (a compound having an aromatic skeleton, manufactured by Tokyo Chemical Industry Co., Ltd.) Polytetramethylene glycol diacrylate (multifunctional (meth)acrylate compound, "PTMGA250" manufactured by Kyoeisha Chemical Co., Ltd.)

[0201] (Coating layer material) Silica (containing silicon atoms, "QSG" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0202] (Colorants) Carbon black (inorganic particles), manufactured by Mitsubishi Materials Corporation Titanium black (inorganic particles), manufactured by Mitsubishi Materials Corporation Manganese oxide (inorganic particles), manufactured by Fuji Pigment Co., Ltd. Azo pigment (organic black pigment), manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Perylene pigment (organic black pigment), manufactured by BASF Fluorescein polymerizable dye (organic black dye), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0203] The particle sizes of carbon black, titanium black, manganese oxide, azo pigments, and perylene pigments were adjusted to the specified particle sizes shown in Tables 1, 3, 5, 7, 9, and 11. The particle size of the fluorescein-based polymerizable dyes was not adjusted because they were used by dissolving them in the polymerizable component.

[0204] (1) Preparation of Resin Particles (Example 1) 5 parts by weight of an azo pigment were added to 89 parts by weight of polypropylene glycol diacrylate, 5 parts by weight of divinylbenzene, 2 parts by weight of isobornyl acrylate, 2 parts by weight of cyclohexyl methacrylate, 1 part by weight of methyl methacrylate, and 1 part by weight of styrene. Next, ultra-high-pressure wet disintegration was performed using an ultra-high-pressure wet atomizer ("Starburst 10" manufactured by Sugino Machine Co., Ltd.) to obtain a monomer mixture. The obtained monomer mixture was diluted with acetone and subjected to laser diffraction particle size distribution measurement. The particle diameter of the colorant (pigment) was found to be 200 nm. 2000 parts by weight of a 2.5 wt% aqueous solution of polyvinyl alcohol with a molecular weight of approximately 2000 dissolved in pure water was placed in a reaction vessel. The obtained monomer mixture was added and stirred to adjust the particle diameter of the monomer droplets to the desired particle diameter. The mixture was then heated at 90°C for 9 hours to polymerize the monomer droplets, yielding particles. The resulting particles were washed several times with hot water and acetone, and then classified to recover the resin particles.

[0205] Examples 2 to 6, 19 to 29, and Comparative Example 1 Resin particles were prepared in the same manner as in Example 1, except that the materials and contents (parts by weight) of the resin particles were changed as shown in Tables 1, 7, and 9.

[0206] (Example 7) Particles obtained in the same manner as in Example 1 were used as base particles, except that the type and content (parts by weight) of the polymerizable component and colorant were changed as shown in Table 3. 10,000 parts by weight of the obtained base particles were dispersed in water, and 97 parts by weight of divinylbenzene and 3 parts by weight of styrene were added, followed by heating and stirring at 80°C for 9 hours to produce resin particles having base particles and a coating layer on the surface of the base particles, and having unevenness on the surface of the resin particle.

[0207] (Examples 8 to 18 and 30 to 35, and Comparative Example 2) Resin particles having base particles and a coating layer on the surface of the base particles were prepared in the same manner as in Example 7, except that the materials and contents (parts by weight) of the base particles and coating layer were changed as shown in Tables 3, 5, and 11.

[0208] For the resin particles of Examples 1 to 35 and Comparative Examples 1 and 2, the following light-control laminates were produced.

[0209] (2) Preparation of light control laminate GHLC type light control laminate: A light control film was prepared in which a known GHLC layer was arranged between two sheets of PET film on which transparent and conductive ITO had been vapor-deposited, except that 5 wt % of the obtained resin particles or the resin particles of Comparative Example 1 were dispersed. A GHLC type light control laminate was prepared by sandwiching the light control film between two sheets of transparent glass.

[0210] PDLC-based light-control laminate: A light-control film was produced in which a known PDLC layer was disposed between two sheets of PET film on which transparent and conductive ITO had been vapor-deposited, except that 5 wt % of the obtained resin particles or the resin particles of Comparative Example 1 were dispersed. A PDLC-based light-control laminate was produced by sandwiching the light-control film between two sheets of transparent glass.

[0211] (Evaluation) (1) Particle diameter of resin particles The particle diameters of approximately 100,000 particles of the obtained resin particles were measured using a particle size distribution measuring device (Multisizer 4 manufactured by Beckman Coulter) to determine the average particle diameter of the resin particles.

[0212] (2) Weather resistance test: In accordance with JIS B7753:2004, a sunshine carbon arc lamp was used at 85°C, 50% RH, wavelength 300 nm to 700 nm, and illuminance 255 W / m ２ 500 hours (accumulated light intensity: 459 MJ / m ２) and a weather resistance test was performed. The sunshine carbon arc lamp used was a "Sunshine Carbon Arc (Open Frame Carbon Arc) Lamp Type Light and Weather Resistance Tester: WEL-300L" manufactured by Suga Test Instruments Co., Ltd. The compression recovery rate at 20% compressive deformation was measured for the resin particles before the weather resistance test and the resin particles after the weather resistance test using the method described above. In addition, the ratio (compression recovery rate of resin particles at 20% compressive deformation after weather resistance test / compression recovery rate of resin particles at 20% compressive deformation before weather resistance test) was calculated, and the value is shown in the column of "Ratio after weather resistance test / compression recovery rate before weather resistance test" in the table.

[0213] (3) 20% Compressive Elastic Modulus The 20% compressive elastic modulus of the obtained resin particles was measured using a Fisherscope H-100 manufactured by Fisher Co., Ltd., by the method described above.

[0214] (4) Dielectric Strength The dielectric strength of the obtained resin particles was measured by the method described above.

[0215] (5) Sphericity when sandwiched between two substrates at a pressure of 0.1 MPa The sphericity of the obtained resin particles when sandwiched between two substrates at a pressure of 0.1 MPa was measured using the method described above.

[0216] (6) Static Angle of Repose The static angle of repose of the obtained resin particles was measured by the method described above.

[0217] (7) Resin Particle Aggregation Inhibition Property The aggregation inhibition property of resin particles was evaluated based on the measured static angle of repose according to the following criteria.

[0218] [Criteria for determining the agglomeration suppression of resin particles] A: static angle of repose is less than 30° B: static angle of repose is 30° or more and less than 40° C: static angle of repose is 40° or more and less than 50° D1: static angle of repose is 50° or more and less than 60° D2: static angle of repose is 60° or more and less than 65° E: static angle of repose is 65° or more

[0219] (8) Conduction reliability of light-control laminate An electric field was applied to the obtained PDLC-type light-control laminate using a "PMX-A" manufactured by Kikusui Electronics Co., Ltd., and the voltage at which conduction occurred was measured. The conduction reliability of the light-control laminate was evaluated according to the following criteria.

[0220] [Criteria for determining the conduction reliability of the light-control laminate] A: No conduction occurs even at 300V or more B: Conduction occurs at 250V or more and less than 300V C: Conduction occurs at 200V or more and less than 250V D1: Conduction occurs at 150V or more and less than 200V D2: Conduction occurs at 100V or more and less than 150V E: Conduction occurs at less than 100V

[0221] (9) Gap Controllability For the obtained light-control laminate, the maximum and minimum distances between the substrates (transparent glass) were measured, and the gap controllability (initial) was evaluated according to the following criteria. In addition, the obtained light-control laminate was irradiated with a sunshine carbon arc lamp at 85°C, 50% RH, wavelength 300 nm to 700 nm, and illuminance 255 W / m ２ 500 hours (accumulated light intensity: 459 MJ / m ２ The light was irradiated under the conditions of (1) and (2). The sunshine carbon arc lamp used was a "Sunshine Carbon Arc (Open Frame Carbon Arc) Lamp Type Light Resistance and Weather Resistance Tester: WEL-300L" manufactured by Suga Test Instruments Co., Ltd. The gap controllability (after 500 hours) of the light-controllable laminate after light irradiation was also evaluated according to the following criteria.

[0222] [Gap controllability evaluation criteria] A: The maximum value of the distance between the substrates is less than 1.05 times the minimum value. B: The maximum value of the distance between the substrates is 1.05 times or more and less than 1.10 times the minimum value. C: The maximum value of the distance between the substrates is 1.10 times or more and less than 1.15 times the minimum value. D: The maximum value of the distance between the substrates is 1.15 times or more and less than 1.20 times the minimum value. E: The maximum value of the distance between the substrates is 1.20 times or more the minimum value.

[0223] The compositions of the resin particles and the results are shown in Tables 1 to 12 below.

[0224] In addition, in Examples 7 to 12, since the coating layer contains inorganic particles or pigments as a colorant, the light leakage suppression ability of the resin particles was improved compared to Examples 13 and 33 to 35, and the display quality of the resulting light-controlling laminate was improved.

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237] DESCRIPTION OF SYMBOLS 1, 1A, 1B... Resin particles 2A, 2B... Base particles 3A, 3B... Coating layers 4, 5, 6... Light control layer 4A... Liquid crystal capsules 4B... Binder 5A... Droplets of light control suspension 5Aa... Dispersion medium 5Ab... Light control particles 5B... Resin matrix 6A... Liquid crystal 6Aa... Oriented liquid crystal 6B... Dichroic dye 7... First substrate 8... Second substrate 11... PDLC-type light control laminate 21... SPD-type light control laminate 31... GHLC-type light control laminate

Claims

1. Using a Sunshine carbon arc lamp, 85°C, 50% RH, illuminance 255 W / m ２ and 500 hours, the ratio of the compression recovery rate of the resin particles at a 20% compressive deformation after the weather resistance test to the compression recovery rate of the resin particles at a 20% compressive deformation before the weather resistance test is 0.50 or more.

2. The resin particles according to claim 1, wherein the resin particles have a dielectric strength of 10 kV / mm or more.

3. The resin particles according to claim 1 or 2, wherein the compression recovery rate of the resin particles after a 20% compressive deformation before the weather resistance test is 30% or more.

4. The resin particles according to any one of claims 1 to 3, wherein the resin particles have a sphericity of 0.55 or more and 0.98 or less when sandwiched between two substrates at a pressure of 0.1 MPa.

5. The resin particles according to any one of claims 1 to 4, which contain a colorant.

6. The resin particles according to claim 5, wherein the particle diameter of said colorant is 500 nm or less.

7. The resin particles according to claim 5 or 6, wherein the colorant comprises carbon black, titanium black, manganese oxide, an organic black pigment, or an organic black dye.

8. The resin particles according to any one of claims 1 to 7, wherein the resin particles have a static angle of repose of 2° or more and 60° or less.

9. The resin particles according to any one of claims 1 to 8, wherein the particle diameter of the resin particles is 1 μm or more and 150 μm or less.

10. The 20% compressive elastic modulus of the resin particles is 1 N / mm ２ More than 5000N / mm ２ The resin particles according to any one of claims 1 to 9, wherein:

11. The resin particle according to any one of claims 1 to 10, comprising a base particle and a coating layer disposed on a surface of the base particle.

12. The resin particle according to claim 11, wherein the coating layer has a thickness of 30 nm or more and 500 nm or less.

13. Resin particles according to claim 11 or 12, wherein the material of the coating layer contains a compound having an aromatic skeleton, a compound having a hydrocarbon group having three or more carbon atoms in the main chain, or a silicon atom.

14. The resin particles according to any one of claims 1 to 13, which have unevenness on the surface of the resin particles.

15. The resin particles according to any one of claims 1 to 14, which are used as a spacer.

16. The resin particles according to claim 15, which are used as spacers in a light-control laminate.

17. A light-controlling laminate comprising a first substrate, a second substrate, and a light-controlling layer disposed between the first substrate and the second substrate, the light-controlling layer comprising the resin particles according to any one of claims 1 to 16.

18. The light control laminate of claim 17, which is a light control laminate other than a liquid crystal display device.

19. The light-control laminate according to claim 17, which is a polymer dispersed liquid crystal type light-control laminate, a suspended particle device type light-control laminate, or a guest-host liquid crystal type light-control laminate.

20. A light-controlling laminate comprising a first substrate, a second substrate, and a light-controlling layer disposed between the first substrate and the second substrate, the resin particles according to any one of claims 1 to 16 being used in the light-controlling layer.

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