Dimmable laminate and resin spacer for dimmable laminate

Abstract

To provide a dimmer laminate capable of effectively suppressing occurrences of color unevenness and light omission.SOLUTION: A dimmer laminate includes a first transparent base material, a second transparent base material, and a dimmer layer arranged between the first transparent base material and the second transparent base material, wherein the dimmer layer contains a resin spacer, the resin spacer is a plurality of resin particles, the resin spacer does not contain resin particles having a particle diameter that is 1.4 times or more of the average particle diameter of the resin particles, or contains 0.0006% or less of the resin particles having the particle diameter that is 1.4 times or more of the average particle diameter of the resin particles, in 100% of the total numbers of the resin particles.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a dimmable laminate having dimming properties, and a resin spacer used in the dimmable laminate. [Background technology]

[0002] Dimmable materials such as dimmable glass and dimmable films have the property of being able to change between a transparent state and an opaque state depending on whether or not voltage is applied, and are materials that can adjust the amount of incident light and haze. Furthermore, dimmable materials are broadly classified into PDLC (Polymer Dispersed Liquid Crystal) type and SPD (Suspended Particle Device) type depending on the mechanism of action of the state change between transparent and opaque states.

[0003] The PDLC method is a method of dispersing liquid crystals in a resin matrix. PDLC methods include configurations where the liquid crystal and resin matrix are dispersed as a continuous phase, and configurations where the liquid crystal is dispersed as liquid crystal capsules within the resin matrix. When no voltage is applied, the orientation of the liquid crystal molecules is not uniform, and due to the difference in refractive index between the resin matrix and the liquid crystal, incident light is scattered within the light-adjusting material, resulting in an opaque state. When a voltage is applied, the liquid crystal molecules align parallel to the electric field. At this point, the refractive index of the resin matrix and the liquid crystal become equal, allowing incident light to pass through the light-adjusting material, resulting in a transparent state. Thus, the PDLC method adjusts light transmittance by utilizing the molecular orientation of the liquid crystal.

[0004] The SPD method involves dispersing a photo-tunable suspension in a resin matrix. The photo-tunable suspension contains photo-tunable particles, which are responsive to electric fields. In the SPD method, when no voltage is applied, the photo-tunable particles dispersed in the suspension absorb, scatter, or reflect light due to Brownian motion, preventing incident light from passing through the photo-tuning material. When a voltage is applied, the photo-tunable particles undergo polarization and align in a direction parallel to the electric field, allowing incident light to pass through the photo-tuning material. Thus, the SPD method allows for adjustment of light transmittance by utilizing the polarization orientation of the photo-tunable particles.

[0005] As an example of the above-mentioned light-adjusting material, Patent Document 1 discloses a resizable, polymer-stabilized, and thermotropic liquid crystal device. The liquid crystal device has a transparent substrate. In the liquid crystal device, the substrate is coated with a liquid crystal component mixture, which is a mixture of multiple liquid crystal components. The liquid crystal component mixture has a clearing point within the ambient temperature range and a freezing point lower than the expected lowest ambient temperature. The liquid crystal device has a thickness defining means for defining the thickness of the coating of the liquid crystal component mixture. The liquid crystal device has a stabilizing polymer provided on the substrate to bond with the liquid crystal component mixture. The stabilizing polymer cures under the influence of external stimuli.

[0006] Furthermore, Patent Documents 2 and 3 below disclose a dimming film in which a liquid crystal layer is sandwiched between a first laminate and a second laminate, each having at least an alignment layer, and transmitted light is controlled by controlling the orientation of the liquid crystal in the liquid crystal layer by driving electrodes provided on the first laminate or the second laminate.

[0007] In the dimming film described in Patent Document 2, a first region and a second region with different thicknesses are provided in the liquid crystal layer by arranging two or more types of spacers, the difference in thickness in the thickness direction of the liquid crystal layer being 0.1 μm or more and 0.6 μm or less.

[0008] In the dimming film described in Patent Document 3, the first laminate is a laminate in which a bead spacer is provided on a substrate made of a transparent film material to maintain the thickness of the liquid crystal layer. The Vickers hardness value B of the portion of the second laminate in contact with the bead spacer is 11.8 or more and 35.9 or less. When the first laminate is viewed from above, the product of the occupancy rate A, which is the ratio of the area occupied by the bead spacer on the first laminate, and the Vickers hardness value B, A × B, is 0.42 or more.

[0009] Furthermore, Patent Document 4 discloses a dimmable film comprising a first laminate with an alignment layer, a second laminate with an alignment layer, a liquid crystal layer, a spacer, and an electrode, wherein the orientation of liquid crystal molecules is controlled by driving the electrode to control transmitted light. The liquid crystal layer is sandwiched between the first and second laminates and contains liquid crystal molecules. The spacer maintains the thickness of the liquid crystal layer. The electrode is provided on either the first or second laminate. In the dimmable film, the spacer is a transparent bead spacer. The ratio of the spacer's area per unit area when the dimmable region of the liquid crystal layer is viewed from the front is 0.1% to 10%. The liquid crystal layer is a guest-host type liquid crystal layer containing a dichroic dye. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] WO2011 / 123457A1 [Patent Document 2] Japanese Patent Publication No. 2017-198744 [Patent Document 3] Japanese Patent Publication No. 2017-198732 [Patent Document 4] Japanese Patent Publication No. 2017-187810 [Overview of the project] [Problems that the invention aims to solve]

[0011] In dimmable materials such as dimmable glass and dimmable films, spacers are sometimes used to maintain a constant gap between substrates on which the dimmable layer is placed. In conventional dimmable materials, such as those described in Patent Documents 1-4, the uniformity of the gap between substrates in the dimmable material cannot be ensured due to large variations in the particle size of the spacers, which can result in uneven coloring.

[0012] Furthermore, with conventional light-adjusting materials, the inclusion of large particle-sized spacers can cause unevenness on the surface of the light-adjusting material, cracking of the substrate or light-adjusting layer, or tilting of the substrate. As a result, color unevenness or a phenomenon called "light leakage" (where light passes through the spacers) may occur in the light-adjusting material.

[0013] Furthermore, dimmable materials are sometimes used in vehicle applications or building material applications. The area of ​​dimmable materials used in vehicle or building material applications is relatively large. Also, the area of ​​dimmable materials used in building material applications is often larger than that of dimmable materials used in vehicle applications, etc. In large-area dimmable materials, the effects of variations in the particle size of the spacers are significant, which can easily lead to cracking of the substrate or dimmable layer, as well as tilting of the substrate, resulting in uneven color and light leakage in the dimmable material.

[0014] The object of the present invention is to provide a dimmable laminate that can effectively suppress the occurrence of color unevenness and light loss. Another object of the present invention is to provide a resin spacer for a dimmable laminate that can effectively suppress the occurrence of color unevenness and light loss. [Means for solving the problem]

[0015] According to a broad aspect of the present invention, there is provided a dimming laminate including a first transparent substrate, a second transparent substrate, and a dimming layer disposed between the first transparent substrate and the second transparent substrate, wherein the dimming layer includes a resin spacer, the resin spacer is a plurality of resin particles, and the resin spacer does not include resin particles having a particle diameter of 1.4 times or more of the average particle diameter of the resin particles, or includes resin particles having a particle diameter of 1.4 times or more of the average particle diameter of the resin particles at 0.0006% or less among all 100% of the resin particles.

[0016] In a specific aspect of the dimming laminate according to the present invention, the resin spacer does not include resin particles having a particle diameter of 1.7 times or more of the average particle diameter of the resin particles.

[0017] In a specific aspect of the dimming laminate according to the present invention, the resin spacer does not include resin particles having a particle diameter of 0.5 times or less of the average particle diameter of the resin particles, or includes resin particles having a particle diameter of 0.5 times or less of the average particle diameter of the resin particles at 0.5% or less among all 100% of the resin particles.

[0018] In a specific aspect of the dimming laminate according to the present invention, the average particle diameter of the resin particles is 3 μm or more and 100 μm or less.

[0019] In a specific aspect of the dimming laminate according to the present invention, the resin particles include a pigment or a dye.

[0020] In a specific aspect of the dimming laminate according to the present invention, the resin particles include a pigment.

[0021] According to a broad aspect of the present invention, there is provided a resin spacer for a dimming laminate, which is a plurality of resin particles, and does not include resin particles having a particle diameter of 1.4 times or more of the average particle diameter of the resin particles, or includes resin particles having a particle diameter of 1.4 times or more of the average particle diameter of the resin particles at 0.0006% or less among all 100% of the resin particles.

[0022] In a specific surface of the resin spacer for dimmable laminate according to the present invention, it contains 1 million or more of the resin particles. [Effects of the Invention]

[0023] The light-adjustable laminate according to the present invention comprises a first transparent substrate, a second transparent substrate, and a light-adjustable layer disposed between the first transparent substrate and the second transparent substrate. In the light-adjustable laminate according to the present invention, the light-adjustable layer includes a resin spacer. In the light-adjustable laminate according to the present invention, the resin spacer is a plurality of resin particles. In the light-adjustable laminate according to the present invention, the resin spacer does not contain any resin particles having a particle diameter of 1.4 times or more the average particle diameter of the resin particles, or contains 0.0006% or less of resin particles having a particle diameter of 1.4 times or more the average particle diameter of the resin particles out of 100% of the total number of resin particles. Because the light-adjustable laminate according to the present invention is provided with the above configuration, the occurrence of color unevenness and light leakage can be effectively suppressed.

[0024] The resin spacer for a dimmable laminate according to the present invention is composed of multiple resin particles. The resin spacer for a dimmable laminate according to the present invention does not contain any resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles, or it contains 0.0006% or less of resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles out of 100% of the total number of resin particles. Because the resin spacer for a dimmable laminate according to the present invention is provided with the above configuration, the occurrence of color unevenness and light leakage can be effectively suppressed. [Brief explanation of the drawing]

[0025] [Figure 1] Figure 1 is a schematic cross-sectional view showing a PDLC-type dimmable laminate according to the first embodiment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing a dimmable laminate using the SPD method according to a second embodiment of the present invention. [Modes for carrying out the invention]

[0026] The present invention will be described in detail below.

[0027] (Dimmable laminate) The dimmable laminate according to the present invention comprises a first transparent substrate, a second transparent substrate, and a dimmable layer disposed between the first transparent substrate and the second transparent substrate. In the dimmable laminate according to the present invention, the dimmable layer includes a resin spacer. In the dimmable laminate according to the present invention, the resin spacer is a plurality of resin particles. In the dimmable laminate according to the present invention, the resin spacer is an aggregate of a plurality of resin particles, or a powder of a plurality of resin particles.

[0028] In the dimmable laminate according to the present invention, the resin spacer does not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles, or contains 0.0006% or less (6 or less per 1 million particles, 3 or less per 500,000 particles) of resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles out of 100% of the total number of resin particles. If there are 6 or fewer resin particles with a particle diameter 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles, then there are 1.2 or less per 200,000 particles.

[0029] For example, in the dimmable laminate according to the present invention, the resin spacer does not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles, or contains 6 or fewer resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles. Note that if there is 1 resin particle having a particle diameter 1.4 times or more the average particle diameter of the resin particles per 10,000 resin particles, then there are 100 resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles.

[0030] The dimmable laminate according to the present invention has the above configuration, so it can effectively suppress the occurrence of color unevenness and light loss.

[0031] In the dimmable laminate according to the present invention, the resin spacer may contain 500,000 or more resin particles, or 1,000,000 or more resin particles.

[0032] Furthermore, the dimmable laminate according to the present invention may have curved portions. The dimmable laminate according to the present invention may be used in a state having curved portions. In the dimmable laminate according to the present invention, the transparent substrate may have curved portions, and may be used in a state having curved portions. When conventional dimmable materials have curved portions, it is extremely difficult to ensure uniformity of the gaps between substrates in the dimmable material. Also, when conventional dimmable materials have curved portions, they are greatly affected by variations in the particle size of the resin particles, so cracking of the substrate and dimmable layer, and tilting of the substrate become more pronounced than in flat portions, making it extremely difficult to suppress the occurrence of color unevenness and light leakage. However, since the dimmable laminate according to the present invention is provided with the above configuration, even when the dimmable laminate has curved portions, the particle size of the resin particles is uniform, so uniformity of the gaps between substrates can be ensured, and cracking of the substrate and dimmable layer, and tilting of the substrate can be effectively suppressed. As a result, the occurrence of color unevenness and light leakage can be effectively suppressed. In cases where the dimmable laminate according to the present invention has a curved portion, the curvature of the curved portion of the dimmable laminate is preferably 300R or more and 1800R or less. When the curvature of the curved portion of the dimmable laminate satisfies the above preferred embodiment, uniformity of the gap between substrates can be ensured, and cracking of the substrate or dimmable layer, as well as tilting of the substrate, can be suppressed more effectively. As a result, the occurrence of color unevenness and light leakage can be suppressed more effectively.

[0033] To further enhance the effects of the present invention, the light-adjusting laminate preferably has a curved portion and is preferably used in a state having a curved portion. The light-adjusting laminate preferably has a bent or curved shape and is preferably used in a bent or curved shape. The light-adjusting laminate may have a bent portion or a curved portion. The light-adjusting laminate and the transparent substrate preferably have flexibility so that they can be made into a bent or curved shape.

[0034] The transparent substrate described above is, for example, a substrate that is light-transmitting (light-transmitting substrate). For example, light is transmitted from one side of the transparent substrate to the other side through the transparent substrate. For example, when a substance on the other side of the transparent substrate is viewed from one side of the transparent substrate through the transparent substrate, the substance is visible. Transparency also includes, for example, semi-transparent materials. The transparent substrate may be colorless and transparent, or it may be colored and transparent.

[0035] The above-mentioned dimmable laminate may be a dimmable film or dimmable glass. Furthermore, the above-mentioned dimmable laminate may be a dimmable laminate in which the dimmable film is sandwiched between transparent substrates such as glass.

[0036] Next, specific embodiments of the present invention will be described with reference to the drawings.

[0037] Figure 1 is a schematic cross-sectional view showing a PDLC-type dimmable laminate according to the first embodiment of the present invention. Figure 2 is a schematic cross-sectional view showing a SPD-type dimmable laminate according to the second embodiment of the present invention. Note that in Figures 1 and 2, the size, thickness, shape, and amount of dimmable layer and resin spacer have been appropriately modified from the actual size and shape for illustrative purposes.

[0038] The PDLC-type dimmable laminate 1 shown in Figure 1 comprises a first substrate 2, a second substrate 3, and a dimmable layer 4. The dimmable layer 4 is sandwiched between the first substrate 2 and the second substrate 3. The dimmable layer 4 is positioned between the first substrate 2 and the second substrate 3. A sealant (not shown) may be placed around the dimmable layer 4 between the first substrate 2 and the second substrate 3.

[0039] The dimming layer 4 includes a liquid crystal capsule 4A, a binder 4B, and a resin spacer 6. The resin spacer 6 is an aggregate of multiple resin particles, or a powder of multiple resin particles. These resin particles function as spacers. The liquid crystal capsule 4A is a liquid crystal material. The liquid crystal capsule 4A is dispersed in the binder 4B. The liquid crystal capsule 4A is held in a capsule-like form within the binder 4B. The liquid crystal material may be dispersed in the binder in a capsule-like form, or the liquid crystal material may be dispersed in the binder as a continuous phase.

[0040] The resin spacer 6 is used as a resin spacer for a dimmable laminate. The resin spacer 6 is in contact with the first substrate 2 and the second substrate 3. The resin spacer 6 controls the gap between the first substrate 2 and the second substrate 3.

[0041] Transparent electrodes are formed on the surface of the first substrate 2 and the surface of the second substrate 3 (not shown). Examples of materials for the transparent electrodes include indium tin oxide (ITO).

[0042] When no voltage is applied to the PDLC-type dimmable laminate 1, the orientation of the liquid crystal molecules within the liquid crystal capsule 4A is not uniform. Due to the difference in refractive index between the binder 4B and the liquid crystal material, the incident light is scattered within the binder, resulting in an opaque state.

[0043] When a voltage is applied to the PDLC-type dimmable laminate 1, the liquid crystal molecules in the liquid crystal capsule 4A align in a direction parallel to the electric field. In this state, if the refractive index of the binder 4B and the liquid crystal material become equal, light can be transmitted, resulting in a transparent state.

[0044] The SPD-type dimmable laminate 11 shown in Figure 2 comprises a first substrate 2, a second substrate 3, and a dimmable layer 5. The dimmable layer 5 is sandwiched between the first substrate 2 and the second substrate 3. The dimmable layer 5 is positioned between the first substrate 2 and the second substrate 3.

[0045] The light-adjusting layer 5 includes droplets 5A of a light-adjusting suspension, a resin matrix 5B, and a resin spacer 6. The resin spacer 6 is an aggregate of multiple resin particles, or a powder of multiple resin particles. These resin particles function as spacers. The droplets 5A of the light-adjusting suspension are dispersed in the resin matrix 5B. The droplets 5A of the light-adjusting suspension are held in droplet form within the resin matrix 5B.

[0046] A droplet 5A of the light-modulated suspension contains a dispersion medium 5Aa and light-modulated particles 5Ab. The light-modulated particles 5Ab are dispersed in the dispersion medium 5Aa.

[0047] The resin spacer 6 is used as a resin spacer for a dimmable laminate. The resin spacer 6 is in contact with the first substrate 2 and the second substrate 3. The resin spacer 6 controls the gap between the first substrate 2 and the second substrate 3.

[0048] Transparent electrodes are formed on the surface of the first substrate 2 and the surface of the second substrate 3 (not shown). Examples of materials for the transparent electrodes include indium tin oxide (ITO).

[0049] When no voltage is applied to the SPD-type dimming laminate 11, the incident light is absorbed, scattered, or reflected by the light-adjusting particles 5Ab dispersed in the dispersion medium 5Aa constituting the droplet 5A of the light-adjusting suspension due to Brownian motion of the light-adjusting particles 5Ab. As a result, the incident light cannot pass through the dimming layer 5, and the layer becomes opaque.

[0050] When a voltage is applied to the SPD-type dimming laminate 11, the light-adjusting particles 5Ab align in a direction parallel to the electric field. As a result, incident light can pass between the aligned light-adjusting particles 5Ab, resulting in a transparent state.

[0051] Further details of the present invention are described below.

[0052] (Resin spacer) The resin spacer according to the present invention is preferably a resin spacer used in a light-adjustable laminate. Specifically, the resin spacer for a light-adjustable laminate according to the present invention is preferably a resin spacer used in a light-adjustable laminate comprising a first transparent substrate, a second transparent substrate, and a light-adjustable layer disposed between the first transparent substrate and the second transparent substrate. The resin spacer for a light-adjustable laminate according to the present invention is a plurality of resin particles. The resin spacer for a light-adjustable laminate according to the present invention does not contain resin particles having a particle diameter of 1.4 times or more the average particle diameter of the resin particles, or contains 0.0006% or less of resin particles having a particle diameter of 1.4 times or more the average particle diameter of the resin particles out of 100% of the total number of resin particles.

[0053] For example, the resin spacer according to the present invention does not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles, or contains 6 or fewer resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles (6 or fewer per 1 million particles, 3 or fewer per 500,000 particles). If there are 6 or fewer resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles, then there are 1.2 or fewer per 200,000 particles.

[0054] The resin spacer according to the present invention has the above configuration, so it can effectively suppress the occurrence of color unevenness and light leakage.

[0055] The resin spacer according to the present invention may contain 500,000 or more of the above-mentioned resin particles, or it may contain 1,000,000 or more of them.

[0056] It is preferable that the above resin spacers contain 0.0006% or less of resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles, more preferably 0.0005% or less, even more preferably 0.0004% or less, and particularly preferably 0.0002% or less (2 or less per 1 million particles) of the total number of resin spacers. It is particularly preferable that the above resin spacers do not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles. The above resin spacers may contain 200,000 or more of the above resin particles, 500,000 or more, or 1,000,000 or more. It is also preferable that the above resin spacers contain 500,000 or more of the above resin particles and do not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles. It is more preferable that the above resin spacers contain 1,000,000 or more of the above resin particles and do not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the above resin particles. When the above resin spacer satisfies the above preferred embodiment, it is possible to more effectively prevent the formation of irregularities on the surface of the dimmable laminate, cracking of the substrate or dimmable layer, and tilting of the substrate. As a result, when the above resin spacer satisfies the above preferred embodiment, it is possible to more effectively suppress the occurrence of color unevenness and light leakage in the dimmable laminate.

[0057] Methods for obtaining resin spacers that satisfy the above preferred embodiments include selecting resin particles having the desired particle size using a classification device. Examples of classification devices include methods using the principle of inertial force and methods utilizing particle size.

[0058] Preferably, the resin spacer does not contain resin particles having a particle diameter 1.5 times or more the average particle diameter of the resin particles, and is particularly preferably free from resin particles having a particle diameter 1.7 times or more the average particle diameter of the resin particles. Preferably, the resin spacer contains 500,000 or more of the resin particles and does not contain resin particles having a particle diameter 1.5 times or more the average particle diameter of the resin particles, and is more preferably free from resin particles having a particle diameter 1.7 times or more the average particle diameter of the resin particles. Preferably, the resin spacer contains 1,000,000 or more of the resin particles and does not contain resin particles having a particle diameter 1.5 times or more the average particle diameter of the resin particles, and is more preferably free from resin particles having a particle diameter 1.7 times or more the average particle diameter of the resin particles. When the above resin spacer satisfies the above preferred embodiment, it is possible to more effectively prevent the formation of irregularities on the surface of the dimmable laminate, cracking of the substrate or dimmable layer, and tilting of the substrate. As a result, when the above resin spacer satisfies the above preferred embodiment, it is possible to more effectively suppress the occurrence of color unevenness and light leakage in the dimmable laminate.

[0059] Methods for obtaining resin spacers that satisfy the above preferred embodiments include selecting resin spacers having the desired particle size using a classification device. Examples of classification devices include methods using the principle of inertial force and methods utilizing particle size.

[0060] It is preferable that the above resin spacer does not contain resin particles having a particle diameter of 0.5 times or less the average particle diameter of the above resin particles, or that it contains 0.5% or less (5 or less per 1000 particles) of resin particles having a particle diameter of 0.5 times or less the average particle diameter of the above resin particles out of 100% of the total number of resin particles. It is more preferable that the above resin spacer contains 0.3% or less (3 or less per 1000 particles) of resin particles having a particle diameter of 0.5 times or less the average particle diameter of the above resin particles out of 100% of the total number of resin particles. It is particularly preferable that the above resin spacer does not contain resin particles having a particle diameter of 0.5 times or less the average particle diameter of the above resin particles. When the above resin spacer satisfies the above preferred embodiments, it is possible to more effectively prevent damage to the substrate in the dimmable laminate and to more effectively improve the dimming performance that adjusts the amount of incident light and haze.

[0061] Methods for obtaining resin spacers that satisfy the above preferred embodiments include selecting resin spacers having the desired particle size using a classification device. Examples of classification devices include methods using the principle of inertial force and methods utilizing particle size.

[0062] From a practical standpoint, the average particle size of the resin particles is preferably 3 μm or more, more preferably 5 μm or more, even more preferably 7 μm or more, preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. When the average particle size of the resin particles is 3 μm or more and 100 μm or less, it can be suitably used in applications such as dimmable laminates.

[0063] The average particle diameter of the resin particles is preferably the number-average particle diameter. The average particle diameter of the resin particles can be determined by any particle diameter measuring device. For example, particle size distribution analyzers that use principles such as laser light scattering, electrical resistance change, or post-imaging image analysis can be used. Specifically, a method for measuring the average particle diameter of the resin particles is to measure the particle diameter of approximately 100,000 resin particles using a particle size distribution analyzer (Beckman Coulter's "Multisizer 4") and then determine the average particle diameter.

[0064] The particle diameter of the above-mentioned resin particles refers to the diameter if the resin particles are spherical, and if the resin particles have a shape other than a perfect sphere, it refers to the diameter assuming they are spherical to the extent of their volume.

[0065] The aspect ratio of the above resin particles is preferably 1.5 or less, more preferably 1.3 or less. There is no particular lower limit to the aspect ratio of the above resin particles. The aspect ratio of the above resin particles may be 1 or more. The aspect ratio of the above resin particles is expressed as major axis / minor axis. When the aspect ratio of the above resin particles is less than or equal to the upper limit above, the above resin spacer can be suitably used in dimmable laminate applications.

[0066] The aspect ratio of the above resin particles can be determined by observing 10 arbitrary resin particles with an electron microscope or optical microscope, defining the maximum and minimum diameters as the major and minor axes, respectively, and calculating the average of the major / minor axis ratio for each resin particle.

[0067] The coefficient of variation (CV value) of the particle size of the resin particles is preferably 10% or less, more preferably 7% or less. There is no particular lower limit to the coefficient of variation (CV value) of the particle size of the resin particles. When the coefficient of variation (CV value) of the particle size of the resin particles is below the upper limit, it is possible to more effectively prevent the formation of irregularities on the surface of the light-adjustable laminate, cracking of the substrate or light-adjustable layer, and tilting of the substrate. As a result, it is possible to more effectively suppress the occurrence of color unevenness and light loss in the light-adjustable laminate.

[0068] The coefficient of variation (CV value) mentioned above can be measured as follows.

[0069] CV value (%) = (ρ / Dn) × 100 ρ: Standard deviation of the particle size of resin particles Dn: Average particle size of resin particles

[0070] The shape of the resin particles is not particularly limited. The resin particles may be spherical, or they may be flattened or have other shapes besides spherical.

[0071] The 10% K value of the above resin particles is preferably 1000 N / mm². 2 More preferably, 3000 N / mm 2 The above is preferable, preferably 10,000 N / mm 2 More preferably, 7000 N / mm 2 The following applies: If the 10%K value of the resin particles is above the lower limit, the gap between substrates in the dimmable laminate can be made even more uniform. If the 10%K value of the resin particles is below the upper limit, damage to the substrates in the dimmable laminate can be prevented more effectively, and the dimming performance for adjusting the amount of incident light and haze can be improved more effectively.

[0072] The 20% K value of the above resin particles is preferably 1000 N / mm². 2 More preferably, 3000 N / mm 2 The above is preferable, preferably 10,000 N / mm 2 More preferably, 7000 N / mm 2 The following applies: If the 20%K value of the resin particles is above the lower limit, the gap between substrates in the dimmable laminate can be made even more uniform. If the 20%K value of the resin particles is below the upper limit, damage to the substrates in the dimmable laminate can be prevented more effectively, and the dimming performance for adjusting the amount of incident light and haze can be improved more effectively.

[0073] The 10%K and 20%K values ​​of the above resin particles can be measured as follows.

[0074] Using a micro-compression tester, one resin particle is compressed on the smooth indenter end face of a cylinder (diameter 100 μm, made of diamond) at 25°C, a compression speed of 0.3 mN / second, and a maximum test load of 20 mN. At this time, the load value (N) and the compression displacement (mm) are measured. From the obtained measurement values, the 10% K value (10% compression elastic modulus) and the 20% K value (20% compression elastic modulus) of the resin particle can be obtained by the following formula. As the above-mentioned micro-compression tester, for example, "Micro Compression Tester MCT-W200" manufactured by Shimadzu Corporation, "Fisher Scope H-100" manufactured by Fisher, etc. are used. The 10% K value and 20% K value of the above resin particles are preferably calculated by arithmetically averaging the 10% K value or 20% K value of 50 arbitrarily selected resin particles.

[0075] 10% K value or 20% K value (N / mm 2 ) = (3 / 2 1 / 2 )·F·S -3 / 2 ·R -1 / 2 F: Load value (N) when the resin particle is 10% compressed or load value (N) when the resin particle is 20% compressed S: Compression displacement (mm) when the resin particle is 10% compressed or compression displacement (mm) when the resin particle is 20% compressed R: Radius (mm) of the resin particle

[0076] The above K value represents the hardness of the resin particle universally and quantitatively. By using the above K value, the hardness of the resin particle can be represented quantitatively and uniquely.

[0077] The compression recovery rate of the above resin particles is preferably 30% or more, more preferably 40% or more, preferably 95% or less, and more preferably 90% or less. When the compression recovery rate of the above resin particles is above the above lower limit and below the above upper limit, in the light control laminate, the gap between the substrates can be made more uniform, and the occurrence of color unevenness can be more effectively suppressed.

[0078] The compression recovery rate of the above resin particles can be measured as follows.

[0079] Resin particles are scattered onto a sample stage. For each scattered resin particle, a microcompression tester is used to apply a load (reverse load value) to the resin particle at 25°C using the smooth end face of a cylindrical (100 μm diameter, diamond) indenter, in the direction of the particle's center, until a load of 1 gf is applied to the particle. Then, the load is removed until the origin load value (0.40 mN) is reached. The load-compression displacement during this time is measured, and the compression recovery rate can be calculated using the following formula. The loading speed is set to 0.33 mN / sec. Examples of microcompression testers used include the Shimadzu Corporation "Microcompression Tester MCT-W200" and the Fischer Scope H-100 from Fischer.

[0080] Compression recovery rate (%) = [L2 / L1] × 100 L1: Compressive displacement from the origin load value to the reverse load value when a load is applied. L2: Unloading displacement from the reversal load value when the load is released to the origin load value.

[0081] The fracture strain of the above resin particles is preferably 30% or more, more preferably 40% or more, preferably 80% or less, and more preferably 70% or less. When the fracture strain of the above resin particles is above the lower limit and below the upper limit, the gap between substrates in the dimmable laminate can be made even more uniform, and the occurrence of color unevenness can be suppressed even more effectively.

[0082] The fracture strain of the above resin particles can be measured as follows.

[0083] Resin particles are scattered on a sample stage. For each scattered resin particle, a load is applied towards the center of the particle using a microcompression tester until the resin particle breaks. The displacement at the time of breakage is then measured. The ratio of the displacement at the time of breakage to the particle diameter is defined as the fracture strain. The loading speed is set to 0.33 mN / sec. Examples of microcompression testers used include the Shimadzu Corporation "Microcompression Tester MCT-W200" and the Fischer AG "Fischerscope H-100".

[0084] The total light transmittance of the above resin particles is preferably 5% or less, more preferably 4% or less. There is no particular lower limit to the total light transmittance of the above resin particles. If the total light transmittance of the above resin particles is below the upper limit, the phenomenon of light transmission from the spacer portion (light leakage) in the dimmable laminate can be prevented more effectively, and the occurrence of color unevenness can be suppressed more effectively.

[0085] The total light transmittance of the above resin particles can be measured as follows.

[0086] A transparent double-sided tape is applied to the surface of a transparent plate (such as a transparent acrylic plate), and resin particles are uniformly spread and adhered to the adhesive surface of the double-sided tape to create an evaluation sample in which the resin particles are arranged in a single layer on the double-sided tape. The total light transmittance is measured using the obtained evaluation sample. The total light transmittance can be measured using a spectrophotometer (such as the "V-670" manufactured by JASCO Corporation). An integrating sphere can be used as a detector.

[0087] From the viewpoint of further preventing the elution and diffusion of impurities, it is preferable that the surface of the resin particles is coated with a coating agent such as a silane coupling agent. The coating film is preferably a monolayer or a polymer film. The resin particles do not necessarily have the above-mentioned coating.

[0088] The above-mentioned silane coupling agents are not particularly limited. Examples of the above-mentioned silane coupling agents include amino-based silane coupling agents such as γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, 3-[N-allyl-N-(2-aminoethyl)]aminopropyltrimethoxysilane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N-allyl-N-methacrylate)aminopropyltrimethoxysilane, and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane; N,N-bis[3-(methyldimethoxysilyl)propyl]amine, N,N-bis[3-(trimethoxysilyl)propyl]amine, and N,N-bis[3-(methyldimethoxysilyl)propyl]ethyl Examples include amide-based silane coupling agents such as didiamine, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N-glycidyl-N,N-bis[3-(methyldimethoxysilyl)propyl]amine, and N-glycidyl-N,N-bis[3-(trimethoxysilyl)propyl]amine; vinyl-based silane coupling agents such as vinyltriethoxysilane and vinyl-tris(2-methoxyethoxy)silane; methacrylic-based silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; glycidyl-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; and mercapto-based silane coupling agents such as γ-mercaptopropyltrimethoxysilane.

[0089] The method for obtaining resin particles by coating a surface with a coating agent is not particularly limited. The following methods can be used to obtain resin particles by coating a surface with a coating agent: A method in which the resin particles (before coating) and the coating agent are mixed in an inorganic solvent such as water or an organic solvent such as alcohol, heated under stirring, the heated resin particles are separated by decantation or the like, and the solvent is removed by vacuum drying or the like. A method in which the resin particles (before coating) and the coating agent are directly mixed and heated.

[0090] The above-mentioned resin spacer is used in a dimmable laminate. The above-mentioned resin spacer may also be used as a spacer for dimmable glass, or as a spacer for dimmable film.

[0091] The above resin particles preferably contain a pigment or dye. The above resin particles preferably have a base particle body and a pigment or dye contained within the base particle body. The above base particle body is preferably a resin particle body, and preferably a resin particle. In this specification, "(meth)acrylate" means one or both of "acrylate" and "methacrylate," and "(meth)acrylic" means one or both of "acrylic" and "methacrylic."

[0092] Various organic materials are suitably used as the material for the resin particles and the base particle body. Examples of materials for the resin particles and the base particle body include polyolefin resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyisobutylene, and polybutadiene; acrylic resins such as polymethyl methacrylate and polymethyl acrylate; polycarbonate, polyamide, phenol formaldehyde resin, melamine formaldehyde resin, benzoguanamine formaldehyde resin, urea formaldehyde resin, phenol resin, melamine resin, benzoguanamine resin, urea resin, epoxy resin, unsaturated polyester resin, saturated polyester resin, polyethylene terephthalate, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyamide-imide, polyetheretherketone, polyethersulfone, divinylbenzene polymer, and divinylbenzene copolymer. Examples of divinylbenzene copolymers include divinylbenzene-styrene copolymer and divinylbenzene-(meth)acrylic acid ester copolymer. Since the compressive deformation characteristics of the above-mentioned resin particles can be easily controlled within a suitable range, it is preferable that the material of the above-mentioned resin particles and the material of the above-mentioned base particle body are polymers obtained by polymerizing one or more polymerizable monomers having ethylenically unsaturated groups.

[0093] When the above resin particles and the above base material particle bodies are obtained by polymerizing a polymerizable monomer having an ethylenically unsaturated group, the polymerizable monomer having an ethylenically unsaturated group can be a non-crosslinked monomer or a crosslinked monomer.

[0094] The above non-crosslinked monomers include vinyl compounds such as styrene monomers like styrene, α-methylstyrene, and chlorostyrene; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether; vinyl acid ester compounds such as vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate; halogen-containing monomers such as vinyl chloride and vinyl fluoride; and (meth)acrylic compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and cyclohexyl Alkyl (meth)acrylate compounds such as (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; olefin compounds such as diisobutylene, isobutylene, linearene, ethylene, and propylene as α-olefin compounds; and isoprene and butadiene as conjugated diene compounds.

[0095] The above crosslinkable monomers include vinyl monomers such as divinylbenzene, 1,4-divinyloxybutane, and divinylsulfone; polyfunctional (meth)acrylate compounds such as tetramethylolmethane tetra(meth)acrylate, polytetramethylene glycol diacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol 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. Examples include triallyl(iso)cyanurate, triallyl trimellitate, diallyl phthalate, diallyl acrylamide, and diallyl ether; as silane compounds, silane alkoxide compounds such as tetramethoxysilane, tetraethoxysilane, 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 include polymerizable double-bond-containing silane alkoxides 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-ended modified silicone oil, two-ended silicone oil, and side-chain type silicone oil; and carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride.

[0096] The resin particles and the base particle bodies described above can be obtained by polymerizing the polymerizable monomer having the ethylenically unsaturated group described above. The resin particles and the base particle bodies described above may also be obtained by uniformly mixing and dispersing a pigment or dye in the polymerizable monomer having the ethylenically unsaturated group and then polymerizing it. The polymerization method described above is not particularly limited and can be polymerized by known methods. Examples of the polymerization method described above include radical polymerization, ionic polymerization, polycondensation (condensation polymerization, condensation polymerization), addition condensation, living polymerization, and living radical polymerization. Specifically, examples include suspension polymerization in the presence of a radical polymerization initiator, and seed polymerization and dispersion polymerization, which are methods in which monomers are swelled together with a radical polymerization initiator using non-crosslinked seed particles.

[0097] To uniformly mix and disperse the pigment or dye in the polymerizable monomer having the above-mentioned ethylenically unsaturated group, a ball mill, bead mill, sand mill, attritor, sand grinder, and nanomizer may be used. In this case, a dispersant may be added to improve the dispersibility of the pigment or dye.

[0098] The above-mentioned dispersant is not particularly limited. Examples of the above-mentioned dispersant include water-soluble polymers such as polyvinyl alcohol, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and sodium poly(meth)acrylate. Furthermore, examples of the above-mentioned dispersant include barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate, calcium phosphate, talc, clay, and metal oxide powder.

[0099] (Pigments or dyes) The resin particles according to the present invention preferably contain a pigment or a dye. The resin particles may contain both a pigment and a dye, only a pigment, or only a dye. The pigment or dye is preferably one that can reduce the total light transmittance of the resin particles to 7% or less. The pigment may be a black pigment, a dark blue pigment, or a dark brown pigment. In the light-adjustable laminate, from the viewpoint of more effectively preventing light leakage and more effectively suppressing color unevenness, the pigment is preferably a black pigment. In the light-adjustable laminate, from the viewpoint of more effectively preventing light leakage and more effectively suppressing color unevenness, the dye is preferably a black dye. The resin particles may contain both a black pigment and a black dye, only a black pigment, or only a black dye.

[0100] Examples of the black pigments mentioned above include carbon black, lamp black, graphite, iron oxide, copper-chromium composite oxide, and copper-chromium-zinc composite oxide. Only one of these black pigments may be used, or two or more may be used in combination.

[0101] Examples of the dark blue pigments mentioned above include copper phthalocyanine, cobalt phthalocyanine, and cobalt aluminate. Only one of these dark blue pigments may be used, or two or more may be used in combination.

[0102] Examples of the dark brown pigments mentioned above include zinc ferrite and iron oxide. Only one of these dark brown pigments may be used, or two or more may be used in combination.

[0103] Examples of the above-mentioned black dyes include pyrazole azo dyes, anilino azo dyes, triphenylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xatene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyromethene dyes, triarylmethane dyes, azomethine dyes, beryllene dyes, perinone dyes, quatalylene dyes, and quinophthalone dyes. Other examples include acid dyes, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and dyes obtained by mixing two or more derivatives thereof to produce black dye. The above-mentioned black dyes may be used individually or in combination of two or more.

[0104] If the above resin particles contain a pigment, the pigment is preferably carbon black, titanium black, aniline black, or iron oxide. Only one type of pigment may be used, or two or more types may be used in combination. In the light-adjustable laminate, from the viewpoint of more effectively preventing light leakage and more effectively suppressing color unevenness, if the above resin particles contain a pigment, the pigment is preferably carbon black.

[0105] The carbon black mentioned above is not particularly limited. Examples of carbon black include channel black, roll black, furnace black, thermal black, Ketjen black, and acetylene black. Only one type of carbon black may be used, or two or more types may be used in combination.

[0106] If the above resin particles contain a dye, the dye is preferably an acidic dye. The above dye may be used alone or in combination of two or more types.

[0107] From the viewpoint of further preventing the elution and diffusion of impurities, if the resin particles contain a pigment, it is preferable that the pigment has a coated surface. It is preferable that the surface of the pigment is coated with a polymer. It is preferable that the surface of the pigment is coated with a polymer. From the viewpoint of further preventing the elution and diffusion of impurities, it is preferable that the surface of the carbon black is coated with a polymer. It is preferable that the surface of the carbon black is coated with a polymer. By using a pigment with a coated surface, even if the amount of pigment added is large, it is possible to effectively prevent a decrease in properties such as the electrical resistance of the resin particles. Furthermore, the coating of the surface improves the dispersibility of the pigment, allowing the resin particles to be colored with a smaller amount of pigment. Examples of materials for coating the surface of the pigment include thermoplastic resins.

[0108] The thermoplastic resins mentioned above are not particularly limited. Examples of thermoplastic resins include alkyd resins, modified alkyd resins, phenolic resins, natural resin-modified phenolic resins, maleic acid resins, natural resin-modified maleic acid resins, fumaric acid resins, ester gums, rosin, petroleum resins, coumarone resins, indene resins, polyester resins, polyimide resins, polyamide resins, polycarbonate resins, polyethylene resins, epoxy resins, phenoxy resins, styrene resins, vinyl resins, acrylic resins, chlorinated rubber, benzoguanamine resins, urea resins, polyolefin resins, ethylene-vinyl acetate copolymers, and urethane resins. Only one type of thermoplastic resin may be used, or two or more types may be used in combination.

[0109] The method of coating the surface of the pigment with the thermoplastic resin is not particularly limited. Examples of methods for coating the surface of the pigment with the thermoplastic resin include pulverizing the pigment using a pulverizing device such as a ball mill in a hydrophobic solvent containing the thermoplastic resin, and emulsifying an aqueous dispersion of the pigment in a hydrophobic solvent containing the thermoplastic resin, followed by removing the water by heating.

[0110] The total content of the above pigments and dyes in 100% by weight of the above resin particles is preferably 2% by weight or more, more preferably 3% by weight or more, preferably 40% by weight or less, and more preferably 20% by weight or less. When the total content of the above pigments and dyes is above the lower limit and below the upper limit, light leakage can be prevented more effectively in the dimmable laminate, and the occurrence of color unevenness can be suppressed more effectively.

[0111] In 100% by weight of the above resin particles, the content of the above pigment is preferably 2% by weight or more, more preferably 3% by weight or more, preferably 10% by weight or less, and more preferably 8% by weight or less. When the content of the above pigment is above the lower limit and below the upper limit, the occurrence of light leakage can be prevented more effectively in the dimmable laminate, and the occurrence of color unevenness can be suppressed more effectively.

[0112] The amount of the dye in 100% by weight of the above resin particles is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 40% by weight or less, and more preferably 20% by weight or less. When the amount of the dye is above the lower limit and below the upper limit, light leakage can be prevented more effectively in the light-adjustable laminate, and the occurrence of color unevenness can be suppressed more effectively.

[0113] (Dimming layer) The light-adjusting layer according to the present invention preferably has light-adjusting properties. Light-adjusting properties refer to the ability to adjust the amount of incident light and haze by changing the light transmittance, etc., depending on whether or not a voltage is applied. The material of the light-adjusting layer is not particularly limited. Any material that has light-adjusting properties may be used for the light-adjusting layer.

[0114] (PDLC method) When the dimmable laminate according to the present invention is of the PDLC type, the dimmable layer preferably includes a binder and a liquid crystal material dispersed in the binder.

[0115] The above liquid crystal material is not particularly limited. Any liquid crystal material may be used as long as it has the property of changing orientation depending on the voltage applied. The liquid crystal material may be dispersed as a continuous phase in the binder, or it may be dispersed in the binder in the form of liquid crystal drops or liquid crystal capsules. Examples of the above liquid crystal material include nematic liquid crystals and cholesteric liquid crystals.

[0116] Examples of materials for the above-mentioned cholesteric liquid crystal include steroid cholesterol derivatives, Schiff base-based, azo-based, azoxy-based, benzoic acid ester-based, biphenyl-based, terphenyl-based, cyclohexyl carboxylic acid ester-based, phenylcyclohexane-based, biphenylcyclohexane-based, pyrimidine-based, dioxane-based, cyclohexylcyclohexane ester-based, cyclohexylethane-based, cyclohexane-based, tran-based, alkenyl-based, stilbene-based, condensed polycyclic-based nematic liquid crystals, and smectic liquid crystals. Furthermore, examples of materials for the above-mentioned cholesteric liquid crystal include materials to which chiral components consisting of optically active materials such as Schiff base-based, azo-based, ester-based, and biphenyl-based materials are added. The above-mentioned cholesteric liquid crystal materials may be used individually or in combination of two or more types.

[0117] The binder described above holds the liquid crystal material and suppresses its flow. The binder is not particularly limited as long as it does not dissolve in the liquid crystal material, has sufficient strength to withstand external forces, and has high transmittance to reflected and incident light. Examples of the binder material include water-soluble polymer materials such as gelatin, polyvinyl alcohol, cellulose derivatives, polyacrylic acid polymers, ethyleneimine, polyethylene oxide, polyacrylamide, polystyrene sulfonate, polyamidine, and isoprene sulfonic acid polymers. Furthermore, examples of the binder material include 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.

[0118] The above binder is preferably crosslinked with a crosslinking agent. The crosslinking agent is not particularly limited as long as it is a compound that forms crosslinks between the binders and hardens, makes the binders sparingly soluble, or makes them insoluble. Examples of the above crosslinking agent include acetaldehyde, glutaraldehyde, glyoxal, potassium alum hydrate of a polyvalent metal salt compound, adipic acid dihydrazide, melamine formalin oligomer, ethylene glycol diglycidyl ether, polyamide epichlorohydrin, and polycarbodiimide. The above crosslinking agent may be used alone or in combination of two or more.

[0119] (SPD method) When the photochromic laminate according to the present invention is an SPD type, the photochromic layer preferably includes a resin matrix and a photochromic suspension dispersed in the resin matrix.

[0120] The above-mentioned photo-modified suspension comprises a dispersion medium and photo-modified particles dispersed in the dispersion medium.

[0121] Examples of the above-mentioned light-modulating particles include carbon-based materials such as polyiodides and carbon black, metallic 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 polymers. Only one type of light-modulating particle may be used, or two or more types may be used in combination.

[0122] The above dispersion medium disperses the above light-tuning particles in a flowable state. Preferably, the dispersion medium selectively adheres to the above light-tuning particles, coats them, and acts to cause the above light-tuning particles to move to the droplet phase after phase separation from the resin matrix. Preferably, the dispersion medium is a material that is not electrically conductive and has no affinity for the resin matrix. Furthermore, when the dispersion medium is formed into a light-tuning laminate, it is preferable that the dispersion medium is a liquid copolymer whose refractive index is similar to that of the resin matrix. Preferably, the liquid copolymer is a (meth)acrylic acid ester oligomer having a fluoro group or a hydroxyl group, and more preferably a (meth)acrylic acid ester oligomer having both a fluoro group and a hydroxyl group. When such a copolymer is used, the monomer units of the fluoro group or hydroxyl group are directed toward the light-tuning particles, and the remaining monomer units stabilize the droplets of the light-tuning suspension in the resin matrix. Therefore, the light-tuning particles are easily dispersed in the light-tuning suspension and are easily guided into the droplets after phase separation from the resin matrix.

[0123] Examples of (meth)acrylic acid ester oligomers having the above-mentioned fluoro or hydroxyl groups 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 acrylate. Examples include 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. Furthermore, it is more preferable that these (meth)acrylic acid ester oligomers have both a fluoro group and a hydroxyl group.

[0124] The weight-average molecular weight of the above (meth)acrylic acid ester oligomer is preferably 1000 or more, more preferably 2000 or more, preferably 20000 or less, and more preferably 10000 or less.

[0125] The weight-average molecular weights mentioned above represent the weight-average molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC).

[0126] If the above-mentioned light-adjusting material is of the SPD type, the light-adjusting layer can be manufactured using the resin material for forming the resin matrix and the light-adjusting suspension.

[0127] The above resin material is preferably a resin material that hardens when irradiated with energy rays. Examples of resin materials that harden when irradiated with energy rays include polymer compositions containing a photopolymerization initiator and a polymer compound that hardens when irradiated with energy rays such as ultraviolet light, visible light, or electron beams. Examples of polymer compositions include polymerizable monomers having ethylenically unsaturated groups and polymerizable monomers. Examples of polymerizable monomers having ethylenically unsaturated groups include non-crosslinked monomers and crosslinked monomers.

[0128] Examples of the non-crosslinking monomers mentioned above include the non-crosslinking monomers described above. Examples of the crosslinking monomers mentioned above include the crosslinking monomers described above.

[0129] Examples of the above-mentioned photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-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.

[0130] The above resin material may include organic solvent-soluble resins, thermoplastic resins, and poly(meth)acrylic acid, etc. Furthermore, the above resin material may contain various additives such as color inhibitors, antioxidants, and adhesion promoters, and may also contain solvents.

[0131] (First transparent substrate and second transparent substrate) The materials of the first transparent substrate and the second transparent substrate are not particularly limited. The materials of the first transparent substrate and the second transparent substrate may be the same or different. Examples of the transparent substrate materials include glass and resin films. Examples of the glass include soda-lime glass for general building use, lead glass, borosilicate glass, and glass of various compositions for other applications, as well as functional glass such as heat-reflective 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. Because of their excellent transparency, moldability, adhesiveness, and processability, the transparent substrate is preferably a resin substrate, more preferably a resin film, and even more preferably a polyethylene terephthalate film.

[0132] The transparent substrate described above preferably comprises a substrate body and a transparent conductive film formed on the surface of the substrate body, so that a voltage for dimming can be applied to it. Examples of the transparent conductive film include indium tin oxide (ITO), SnO2, and In2O3.

[0133] From the viewpoint of further improving the visibility of the dimmable laminate, the visible light transmittance of the first transparent substrate and the second transparent substrate is preferably 75% or more, more preferably 80% or more.

[0134] The visible light transmittance of the above transparent substrate can be measured by spectroscopic measurement or other methods in accordance with ISO 13837 (2008).

[0135] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples. Examples 1, 3, and 5 are for reference only.

[0136] (Example 1) (1) Resin spacer Fabrication of resin spacer 1: 1000 parts by weight of divinylbenzene (96% purity) was mixed with 20 parts by weight of benzoyl peroxide and stirred until uniformly dissolved to obtain a monomer mixture. 4000 parts by weight of a 2% aqueous solution of polyvinyl alcohol with a molecular weight of approximately 1700 dissolved in pure water was placed in a reaction vessel. The obtained monomer mixture was added to this and stirred for 4 hours to adjust the particle size so that the monomer droplets reached a predetermined particle size. After this, the reaction was carried out for 9 hours under a nitrogen atmosphere at 90°C to perform a polymerization reaction of the monomer droplets and obtain particles. The obtained particles were washed several times with hot water, methanol, and acetone, respectively, and then classified. After drying overnight at 55°C, the particles were crushed and passed through a stainless steel mesh sieve to obtain resin spacer 1 containing multiple resin particles. The average particle size of resin spacer 1 was 15.9 μm.

[0137] (2) Dimmable laminate Fabrication of a PDLC-type dimmable laminate 1: A light-adjustable film was fabricated by placing a known PDLC layer between two PET films coated with transparent and conductive ITO, with a 5% by weight resin spacer 1 dispersed between them. A PDLC-type light-adjustable laminate 1 was fabricated by sandwiching the light-adjustable film between two transparent glass sheets (no curved surface).

[0138] Fabrication of PDLC-type dimmable laminate 2: A PDLC-type dimmable laminate 2 was fabricated by sandwiching a dimmable film made in the above-described PDLC-type dimmable laminate 1 between two transparent curved glass sheets with a radius of 3 mm (curved surface (curved shape): Yes).

[0139] The PDLC-type dimmable laminates 1 and 2 can be manufactured, for example, by the method described in Japanese Patent Application Publication No. 2013-148744.

[0140] Fabrication of SPD-type dimmable laminate 1: A light-adjustable film was fabricated by placing a known SPD layer between two PET films coated with transparent and conductive ITO, with a 5% by weight resin spacer 1 dispersed between them. An SPD-type light-adjustable laminate 1 was fabricated by sandwiching the light-adjustable film between two transparent glass sheets (no curved surface).

[0141] Fabrication of SPD-type dimmable laminate 2: A dimmable film made using the above SPD method dimmable laminate 1 was sandwiched between two 3mmR transparent curved glass sheets to create an SPD method dimmable laminate 2 (curved surface (curved shape): present).

[0142] The SPD-type dimmable laminates 1 and 2 can be manufactured, for example, by the method described in Japanese Patent Application Publication No. 2014-089361.

[0143] (Example 2) Fabrication of resin spacer 2: Carbon black coated with a polymer was prepared. 5 parts by weight of this carbon black, 47.5 parts by weight of divinylbenzene, and 47.5 parts by weight of tetramethylolmethane triacrylate were mixed to obtain a dispersion. 20 parts by weight of benzoyl peroxide was added to this dispersion and mixed uniformly to obtain a mixture. The obtained mixture was added to 8500 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol, stirred thoroughly, and then homogenized to achieve a predetermined emulsion diameter.

[0144] This emulsion was transferred to a 20-liter reaction vessel equipped with a thermometer, stirrer, and reflux condenser, and the polymerization reaction was carried out at 85°C for 7 hours while stirring in a nitrogen atmosphere, followed by further polymerization at 90°C for 3 hours.

[0145] The polymerization reaction solution was cooled, and the resulting particles were washed with water, methanol, and acetone in that order. After classification and drying overnight at 55°C, the particles were crushed and passed through a stainless steel mesh sieve to obtain resin spacer 2 containing multiple resin particles. The average particle size of resin spacer 2 was 15.0 μm.

[0146] The dimmable laminate was fabricated in the same manner as in Example 1, except that resin spacer 2 was used instead of resin spacer 1 during the fabrication of the dimmable laminate.

[0147] (Example 3) Fabrication of resin spacer 3: Resin spacer 3 was obtained in the same manner as resin spacer 2, except that the average particle size was 6.9 μm.

[0148] The laminated dimming laminate was fabricated in the same manner as in Example 1, except that resin spacer 3 was used instead of resin spacer 1 during the fabrication of the dimming laminate.

[0149] (Example 4) Fabrication of resin spacer 4: Resin spacer 4 was obtained in the same manner as resin spacer 2, except that the average particle size was 30.2 μm.

[0150] The laminated dimming laminate was fabricated in the same manner as in Example 1, except that resin spacer 4 was used instead of resin spacer 1 during the fabrication of the dimming laminate.

[0151] (Example 5) Fabrication of resin spacer 5: Resin spacer 5 was obtained in the same manner as resin spacer 1, except that the average particle size was 80.1 μm.

[0152] In Example 5, the dimmable laminate was fabricated in the same manner as in Example 1, except that resin spacer 5 was used instead of resin spacer 1 during the fabrication of the dimmable laminate. In Example 5, only SPD-type dimmable laminates were fabricated and evaluated.

[0153] (Comparative Example 1) When fabricating the dimmable laminate, a dimmable laminate was fabricated in the same manner as in Example 1, without using a resin spacer.

[0154] (Comparative Example 2) Silica spacer: Micropearl SI-H100 (average particle size 10.0 μm) manufactured by Sekisui Chemical Co., Ltd. The dimmable laminate was fabricated in the same manner as in Example 1, except that a silica spacer was used instead of resin spacer 1.

[0155] (Comparative Example 3) Fabrication of resin spacer A: A resin spacer containing multiple resin particles was prepared in the same manner as in Example 1, except that a classification operation was not performed during the preparation of the resin spacer. The average particle size of resin spacer A was 16.3 μm.

[0156] The dimmable laminate was fabricated in the same manner as in Example 1, except that resin spacer A was used instead of resin spacer 1 during the fabrication of the dimmable laminate.

[0157] (Comparative Example 4) Fabrication of resin spacer B: A resin spacer containing multiple resin particles was prepared in the same manner as in Example 2, except that a classification operation was not performed during the preparation of the resin spacer. The average particle size of resin spacer B was 15.3 μm.

[0158] The dimmable laminate was fabricated in the same manner as in Example 1, except that resin spacer B was used instead of resin spacer 1 during the fabrication of the dimmable laminate.

[0159] (Comparative Example 5) Fabrication of resin spacer C: During the preparation of the resin spacers, resin spacer C containing multiple resin particles was prepared by mixing resin spacer 2 (99% by weight) and resin spacer B (1% by weight). The average particle size of resin spacer C was 15.1 μm.

[0160] The dimmable laminate was fabricated in the same manner as in Example 1, except that resin spacer C was used instead of resin spacer 1 during the fabrication of the dimmable laminate.

[0161] (evaluation) (1) Average particle size The obtained resin spacers were analyzed using a particle size distribution analyzer (Beckman Coulter's "Multisizer 4") to measure the particle size of approximately 100,000 resin particles, and the average particle size was calculated.

[0162] (2) Presence of resin spacer The obtained resin spacers were analyzed using a particle size distribution analyzer (Beckman Coulter's "Multisizer 4") to measure the particle size of 1 million resin particles.

[0163] From the measurement results of the average particle diameter of the resin particles obtained in (1) above, the number of resin particles with a particle diameter of 1.4 times or more the average particle diameter of the resin particles per 1 million resin particles, and the number of resin particles with a particle diameter of 1.7 times or more the average particle diameter of the resin particles per 1 million resin particles were calculated.

[0164] Furthermore, the particle size of 1000 resin particles was measured using a particle size distribution analyzer (Beckman Coulter's "Multisizer 4") for the obtained resin spacers.

[0165] From the measurement results of the average particle diameter of the resin particles obtained in (1) above, the number of resin particles with a particle diameter of 0.5 times or less the average particle diameter of the resin particles per 1000 resin particles was calculated.

[0166] (3) CV value The CV value of the particle size of the obtained resin particles was calculated using the method described above.

[0167] (4) 10%K value and 20%K value The obtained resin particles were measured using a Fischerscope H-100 manufactured by Fischer GmbH, and the 10%K and 20%K values ​​of the resin particles were measured using the method described above.

[0168] (5) Compression recovery rate The compression recovery rate of the obtained resin particles was measured using the FischerScope H-100 manufactured by Fischer GmbH, in the method described above.

[0169] (6) Destructive distortion The fracture strain of the obtained resin particles was measured using a Fischerscope H-100 manufactured by Fischer GmbH, in the method described above.

[0170] (7) Total light transmittance The total light transmittance of the obtained resin particles was measured using the method described above with a JASCO "V-670" instrument.

[0171] (8) Surface roughness (surface irregularities) The surface roughness of the obtained dimmable film was measured using a friction tester (Kato Tech Co., Ltd. "KES-SE"). Specifically, the average friction coefficient and the range of variation of the friction coefficient obtained under a load of 25 gf were measured. Higher values ​​indicate greater surface roughness. Surface roughness was judged according to the following criteria.

[0172] [Criteria for determining surface roughness] ○: Average friction coefficient is less than 0.20, and the variation range of the friction coefficient is less than 0.015. △: Average friction coefficient is 0.20 or higher and less than 0.25, and the variation range of the friction coefficient is 0.015 or higher and less than 0.02. △△: Does not meet any of the criteria of ○, △, or ×. ×: Average friction coefficient is 0.25 or higher, or the range of friction coefficient variation is 0.02 or higher.

[0173] (9) Uneven color The resulting dimmable laminates were visually evaluated to determine whether or not color unevenness had occurred. Color unevenness was judged according to the following criteria.

[0174] [Criteria for judging color unevenness] ○: No color unevenness has occurred. △: Very slight color unevenness is present (no problem in actual use) ×: Uneven coloring has occurred.

[0175] (10) Light leakage The resulting dimmable laminates were visually evaluated to determine whether or not light loss occurred. Light loss was determined according to the following criteria.

[0176] [Criteria for determining light loss] ○: No light leakage has occurred. △: There is a very slight light loss (no problem in actual use). ×: Light loss is occurring.

[0177] (11) Light-adjusting performance (haze) For the obtained dimmable laminates, the haze was calculated both with and without applied voltage. The haze was measured using a Tokyo Denshoku "Haze Meter TC-H3PDK". The obtained haze was evaluated as the dimming performance of the dimmable laminate. The dimming performance was judged according to the following criteria.

[0178] [Criteria for determining dimming performance (haze) (when no voltage is applied)] ○: Haze is 98% or higher △: Haze is 95% or higher, but less than 98%. ×: Haze is less than 95%

[0179] [Criteria for determining dimming performance (haze) (when voltage is applied)] ○: Haze is less than 4% △: Haze is 4% or more, but less than 6%. ×: Haze is 6% or more

[0180] The results are shown in Tables 1-4 below.

[0181] [Table 1]

[0182] [Table 2]

[0183] [Table 3]

[0184] [Table 4] [Explanation of Symbols]

[0185] 1…PDLC type dimmable laminate 2…First substrate 3…Second base material 4,5…Dimming layer 4A...Liquid crystal capsule 4B... Binder 5A... Droplets of light-modulated suspension 5Aa...Dispersion medium 5Ab…Light adjustment particle 5B…Resin matrix 6… Resin spacer 11…SPD type dimmable laminate

Claims

1. The device comprises a first transparent substrate, a second transparent substrate, and a light-adjusting layer disposed between the first and second transparent substrates. The dimming layer includes a resin spacer, The aforementioned resin spacer is a plurality of resin particles, The material of the aforementioned resin particles includes a divinylbenzene-(meth)acrylic acid ester copolymer. The 20% K value of the aforementioned resin particles is 3000 N / mm² or more and 7000 N / mm². ２ The following: The average particle size of the resin particles is 7 μm or more. The total light transmittance of the aforementioned resin particles is 5% or less. The resin spacer does not contain resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles, or contains 0.0006% or less of resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles out of 100% of the total number of resin particles. A dimmable laminate having a curved surface with a curvature of 300R or more and 1800R or less.

2. The light-adjustable laminate according to claim 1, wherein the resin spacer does not contain resin particles having a particle diameter 1.7 times or more the average particle diameter of the resin particles.

3. The dimmable laminate according to claim 1 or 2, wherein the resin spacer does not contain resin particles having a particle diameter of 0.5 times or less the average particle diameter of the resin particles, or contains 0.5% or less of resin particles having a particle diameter of 0.5 times or less the average particle diameter of the resin particles out of 100% of the total number of resin particles.

4. The light-adjustable laminate according to any one of claims 1 to 3, wherein the average particle size of the resin particles is 7 μm or more and 100 μm or less.

5. The light-adjustable laminate according to any one of claims 1 to 4, wherein the resin particles contain a pigment or a dye.

6. The light-adjustable laminate according to claim 5, wherein the resin particles contain a pigment.

7. It consists of multiple resin particles, The material of the aforementioned resin particles includes a divinylbenzene-(meth)acrylic acid ester copolymer. The 20% K value of the aforementioned resin particles is 3000 N / mm² or more and 7000 N / mm². ２ The following: The average particle size of the resin particles is 7 μm or more. The total light transmittance of the aforementioned resin particles is 5% or less. Either the resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles are not included, or the resin particles having a particle diameter 1.4 times or more the average particle diameter of the resin particles are included at a rate of 0.0006% or less of the total number of resin particles. A resin spacer for a dimmable laminate, which is used in a dimmable laminate having a curved surface with a curvature of 300R or more and 1800R or less.

8. The resin spacer for a dimmable laminate according to claim 7, comprising 1 million or more of the aforementioned resin particles.

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