WO2009139444A1 - 光調整粒子の製造方法及び該製造方法で得られた光調整粒子を用いた調光フィルム - Google Patents
光調整粒子の製造方法及び該製造方法で得られた光調整粒子を用いた調光フィルム Download PDFInfo
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- WO2009139444A1 WO2009139444A1 PCT/JP2009/059000 JP2009059000W WO2009139444A1 WO 2009139444 A1 WO2009139444 A1 WO 2009139444A1 JP 2009059000 W JP2009059000 W JP 2009059000W WO 2009139444 A1 WO2009139444 A1 WO 2009139444A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/17—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on variable-absorption elements not provided for in groups G02F1/015 - G02F1/169
- G02F1/172—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on variable-absorption elements not provided for in groups G02F1/015 - G02F1/169 based on a suspension of orientable dipolar particles, e.g. suspended particles displays
Definitions
- the present invention relates to a method for producing light control particles. More specifically, the present invention relates to a method for producing light control particles used in a light control film whose light transmittance varies depending on the magnitude of an electric field. Moreover, it is related with the light control film using the light control particle
- the light modulating material is a material whose light transmittance changes depending on the magnitude of the applied electric field and the amount of incident light can be adjusted.
- a light control suspension in which light control particles that can respond to an electric field are dispersed is dispersed in a resin matrix to obtain a light control material.
- This light control film is a film using a light control layer in which a light control material in which fine droplets of a light control suspension in which light control particles are dispersed is dispersed in a resin matrix cured by ultraviolet irradiation is formed into a film. It is.
- the light adjusting particles absorb, scatter, or reflect light by Brownian motion in a state where no electric field is applied, and therefore light incident on the film cannot be transmitted.
- the light adjustment particles are arranged in a direction parallel to the electric field due to the polarization of the light adjusting particles, so that light incident on the film starts to be transmitted.
- the amount of transmitted light is adjusted by the response of the light adjusting particles to the electric field (see, for example, Patent Document 1).
- Patent Document 2 As the light control particles, those listed in Patent Document 2 are known, but in recent years, the light control particles disclosed in Patent Document 3 are most commercialized because they are excellent in heat resistance and weather resistance. It is considered close.
- Patent Document 4 discloses a manufacturing method of the light adjusting particles, which is the most preferable and preferable manufacturing method.
- water greatly affects the particle size and shape of the light control particles, the total amount of water present in the reaction system at the time of production must be determined strictly.
- cellulose nitrate added for preventing aggregation of the light control particles or the like is generally commercially available that contains water up to about 5% by mass. Need to ask.
- calcium iodide is usually used by dehydrating an inexpensive hydrate, but it is necessary to accurately determine the amount of water remaining.
- Japanese Patent No. 3434295 Japanese Patent Publication No. 1-334369 Japanese Patent No. 2871837 Japanese Patent No. 3448354
- the light control particles having the optimum particle size and shape as a light control material are efficiently used for moisture that greatly affects the particle size and shape.
- it aims at providing the manufacturing method of the light control particle
- the present invention is as follows.
- a resin matrix comprising a polymer medium that is cured by irradiation with energy rays;
- a method for producing light control particles that can be used for a light control material comprising a dispersion medium and a light control suspension having a light control particle dispersed in a flowable state in the dispersion medium.
- A) elemental molecular iodine, (B) alkaline earth metal iodide and (C) heterocyclic compound in a medium and granulating (A), (B) and (C 50 parts by mass or more and 110 parts by mass or less of methanol are allowed to coexist and react with respect to 100 parts by mass in total.
- a resin matrix formed from a polymer medium that cures when irradiated with energy rays In a light control film comprising a light control layer comprising a light control material comprising a dispersion medium, and a light control suspension having a light control particle dispersed in a flowable state in the dispersion medium, A light control film, wherein the light control particles are obtained by the method for manufacturing light control particles according to any one of the above (1) to (3).
- the present invention there is provided a method for producing light-controlling particles that reduces the influence of moisture and has good reproducibility in the granulation step for obtaining the particle size and shape of light-controlling particles suitable as a light control material It becomes possible to do.
- the method for producing light control particles of the present invention includes a resin matrix composed of a polymer medium that is cured by irradiation with energy rays, and A method for producing light control particles that can be used for a light control material comprising a dispersion medium and a light control suspension having a light control particle dispersed in a flowable state in the dispersion medium.
- a method for producing light control particles that can be used for a light control material comprising a dispersion medium and a light control suspension having a light control particle dispersed in a flowable state in the dispersion medium.
- the light control particles obtained by the method for manufacturing light control particles of the present invention are used for a light control material.
- the light control material in the present invention includes a light control suspension having a dispersion medium and light control particles suspended and dispersed in a fluid state in the dispersion medium, and a polymer medium that is cured by irradiation with energy rays. A resin matrix.
- the light control material is used as a film-shaped light control layer, and the light control film can be formed by sandwiching the light control layer between two transparent conductive substrates.
- a liquid light control suspension is dispersed in the form of fine droplets in a resin matrix made of a solid polymer medium.
- a light control film absorbs, scatters, or reflects light due to the random arrangement of the light adjusting particles in a state where no electric field is applied, so that light incident on the film can hardly be transmitted.
- the light adjusting particles when an electric field is applied to the light control film, the light adjusting particles have an electric dipole moment, and therefore the light adjusting particles are arranged in a direction parallel to the electric field, so that light incident on the film is transmitted.
- the light adjustment particles respond to the applied electric field, thereby adjusting the light transmission amount.
- the light dimming particles needle-like or rod-like particles are preferable.
- the particle size used in the light control film is considered to be preferably the following size from the relationship between the response time with respect to the applied voltage when the light control film is used and the aggregation and precipitation in the light control suspension.
- the major axis of the light control particles is preferably 225 to 625 nm, more preferably 250 to 550 nm, and further preferably 300 to 500 nm.
- the ratio of the major axis to the minor axis of the light control particles is preferably 3 to 8, more preferably 3.3 to 7, and still more preferably 3.6 to 6.
- the major axis and minor axis of the light adjusting particles in the present invention are obtained by photographing the light adjusting particles with an electron microscope such as a scanning electron microscope or a transmission electron microscope, and arbitrarily extracting 50 light adjusting particles from the photographed image,
- the major axis and minor axis of each light control particle can be calculated as an average value.
- the major axis is the length of the longest part of the light control particles projected in the two-dimensional visual field by the photographed image.
- the minor axis is the length of the longest part orthogonal to the major axis.
- a particle size distribution meter using the principle of the photon correlation method or the dynamic light scattering method can be used as a method for evaluating the particle diameter of the light control particles in the present invention.
- the size and shape of the particles are not directly measured, but the equivalent diameter is evaluated on the assumption that the particles are spherical, which is different from the SEM observation.
- the particle diameter of the light control particles Is preferably from 135 to 220 nm, more preferably from 140 to 210 nm, still more preferably from 145 to 205 nm.
- This Z average value is, for example, a measured value of a different particle size distribution meter based on an optical correlation method or a dynamic light scattering method, specifically, an optical adjustment particle measured by an electron microscope such as the transmission electron microscope described above. It is known that it shows a good correlation with the major axis and minor axis, and is suitable as an index for evaluating the particle diameter.
- the elemental molecular iodine (A) used in the present invention is a compound of simple iodine, and is generally represented by I 2 .
- elemental molecular iodine may be input into the reaction system as it is, it is preferable to add the elemental molecular iodine after it is dissolved in the medium. It can also be dissolved in a medium in advance and charged as a solution. This is because, when a solution is used, all molecules can react in a reaction stoichiometry. In this case, the concentration of the solution is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and further preferably 7 to 12% by mass. Further, (A) elemental molecular iodine to be used is not particularly limited, but those that are easily dissolved in a medium such as powder or spherical fine particles are preferable.
- alkyl ester organic solvents are preferable, and specific examples include acetate solvents such as ethyl acetate, butyl acetate, isopentyl acetate, and hexyl acetate.
- the (B) alkaline earth metal iodide used in the present invention is not particularly limited, but calcium, for example, among alkaline earth metals can be used.
- Calcium iodide is hygroscopic, and hydrates are generally inexpensive. However, since they are in a lump, they are difficult to dissolve in organic solvents. Therefore, it is preferable to remove moisture as much as possible by drying it under reduced pressure or heat treatment before dissolving it in an organic solvent.
- the moisture content after moisture removal is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less.
- the calcium iodide thus dried may be charged into the reaction system as a solid, but it is preferable to dissolve the calcium iodide without dissolving in the solvent. It can also be dissolved in a medium in advance and charged as a solution.
- the concentration of this solution is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass.
- the water content of 0 to 1.0% by mass in calcium iodide corresponds to 0 to 0.26 parts by mass with respect to 100 masses in total of (A), (B), and (C). It is difficult to accurately measure this amount of water, and in general, a predetermined amount of calcium iodide is measured by titrating and evaluating the amount of calcium with EDTA2Na (ethylenediaminetetraacetic acid) and the like, and the maximum amount of water is estimated by converting the purity. be able to.
- EDTA2Na ethylenediaminetetraacetic acid
- the medium for dissolving calcium iodide is not particularly limited, and examples thereof include acetate solvents such as ethyl acetate, butyl acetate, isopentyl acetate and hexyl acetate, and alcohols such as methanol.
- acetate solvents such as ethyl acetate, butyl acetate, isopentyl acetate and hexyl acetate
- alcohols such as methanol.
- the (C) heterocyclic compound used in the present invention is not particularly limited, but is preferably a compound represented by the following formula (1).
- R 1 and R 2 each independently represents an alkyl group which is hydrogen or a saturated hydrocarbon, and the carbon number thereof is in the range of 1 to 13
- R 1 and R 2 are preferably, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, and the like.
- Examples include pyrazine-2,5-dicarboxylic acid, which can also be used as a hydrate.
- the compound represented by the above formula (1) may be charged into the reaction system as a solid, or may be charged after being dissolved in a medium. However, since the medium for dissolving the above formula (1) is limited, it may continue to exist as undissolved as long as the particles are increased even after being charged into the reaction system. Examples of the medium used for dissolving the compound represented by the above formula (1) include a mixed solvent with water and a basic aqueous solution.
- the molar ratio of the above (A), (B), (C) used in the method for producing a light control particle of the present invention is not particularly limited, and when used for production at a ratio of X: Y: Z, X: 1.7 to 2.3, Y: 0.7 to 1.3, and Z: 1.7 to 2.3 can be used independently.
- light control particles having a large aspect ratio specifically, light control particles having an aspect ratio of 3 to 8, a major axis of 225 to 625 nm, and a particle size of 135 to 220 nm determined by particle size distribution measurement.
- X: 1.8 to 2.2, Y: 0.8 to 1.2, Z: 1.8 to 2.2, X: 1.9 to 2.1, Y: 0.9 To 1.1 and Z: 1.9 to 2.1 are more preferable.
- the medium used in the method for producing the light control particles of the present invention is not particularly limited as long as it is an organic solvent used for dissolving the above (A), (B), and (C).
- ethyl acetate, butyl acetate It is preferable that at least one acetate solvent such as isopentyl acetate and hexyl acetate is contained. These media may be used alone or in combination of two or more.
- cellulose nitrate is also called nitrocellulose and is a nitrate ester of cellulose, and is not particularly limited. Generally, it is classified according to the content of nitro groups in the step of nitrate conversion of cellulose, but any one is used as long as it is dissolved in an organic solvent as a medium used in the method for producing light control particles of the present invention. be able to. Therefore, when it is charged into the reaction system, it may be a solid or may be once dissolved in an organic solvent.
- the relationship between the cellulose nitrate used in the present invention and the medium mass to be used is not particularly limited, but the total mass of cellulose nitrate is preferably 5 to 20% by mass of the medium mass. In particular, in order to produce light control particles with good reproducibility, 6 to 15% by mass is preferable, 7 to 14% by mass is more preferable, and 8 to 13% by mass is further preferable.
- the above (A) , (B) and (C) are preferably from 90 to 150 parts by weight, more preferably from 100 to 145 parts by weight, even more preferably from 105 to 140 parts by weight, based on a total of 100 parts by weight.
- the amount of water present in the reaction system at the time of manufacture is strong in the size and shape of the particle size of the light control particles to be manufactured. Affect. Therefore, the amount of water contained in the (A) elemental molecular iodine, (B) alkali metal earth iodide, (C) heterocyclic compound, organic solvent as a medium, methanol, and cellulose nitrate is accurately evaluated. Furthermore, it is necessary to empirically determine the amount of water necessary to obtain light control particles having a more preferable particle size and shape.
- the total amount of water necessary to obtain light control particles having a preferred particle size and shape is determined empirically as described above, but when methanol is used within the scope of the present invention, for example, the aspect ratio
- the amount of water for obtaining light control particles having a particle diameter of 135 to 220 nm and 3 to 8, long diameters of 225 to 625 nm and particle size distribution measurement in the particle size distribution measurement is as described in (A), (B) and (C) above. 7.5 to 9.6 parts by mass is preferable with respect to 100 parts by mass in total.
- the amount of water is the sum of the above (A), (B) and (C).
- the amount of water is the sum of the above (A), (B) and (C).
- 7.9 to 9.3 parts by mass is more preferable with respect to 100 parts by mass in total of the above (A), (B), and (C).
- the present invention it is essential to coexist methanol in the step of mixing (A), (B) and (C) in the medium and granulating. Specifically, by using 50 to 110 parts by mass of methanol with respect to a total of 100 parts by mass of the above (A), (B) and (C), the influence of moisture is reduced, and the light control particles can be stably produced. It turns out that it can be manufactured.
- the coexisting methanol is less than 50 parts by mass with respect to 100 parts by mass in total of the above (A), (B), and (C), the influence of moisture tends to be large.
- the coexisting methanol exceeds 110 parts by mass with respect to the total of 100 parts by mass of the above (A), (B), and (C), the aspect ratio of the particles tends to decrease.
- the coexisting methanol is outside the scope of the present invention, specifically, in the case of 5 to 50 parts by mass with respect to the total of 100 parts by mass of the above (A), (B), (C),
- the amount of water for obtaining light control particles having an aspect ratio of 3 to 8, a major axis of 225 to 625 nm, and a light control particle having a particle size of 135 to 220 nm required in the particle size distribution measurement is the above (A), (B), (C ) To 7.3 to 8.7 parts by mass with respect to 100 parts by mass in total.
- the water content is as described above in (A), (B), (C). 7.4 to 8.6 parts by mass with respect to a total of 100 parts by mass, and light adjustment particles having a major axis of 300 to 500 nm and light adjustment particles having a particle diameter of 145 to 205 nm required in particle size distribution measurement are produced.
- the required amount of moisture it can be seen that the influence of moisture is greater than when methanol is used within the range specified in the present invention.
- the light adjusting particle manufacturing method of the present invention can make light adjusting particles having a target particle size and shape stably compared to the conventional method when considering an actual manufacturing process.
- the total amount of moisture is determined empirically as described above, but the range is 3 to 15 masses with respect to a total of 100 mass parts of (A), (B), and (C) as described above. Enter the range of the department. However, this varies within this range depending on the molar ratio of (A), (B), and (C) above, the concentration with respect to the medium, and the amount of cellulose nitrate, and the likelihood width is 2 mass% or less.
- the amount of water required in the present invention also considers the water contained in the above-mentioned (A), (B), (C), cellulose nitrate, and the solvent used as a medium. That is, when used as a hydrate, the water content in the hydrate is taken into account, and when water is contained in the solvent, the water content is also taken into account. It is preferable to subtract them.
- the reaction temperature is preferably 30 to 60 ° C., more preferably 33 to 55 ° C., and more preferably 35 to 50 ° C.
- the apparatus for heating and maintaining the temperature is not particularly limited, and any of a mantle heater, an oil bath, and a water bath may be used.
- the order of adding each component is not particularly limited. Is preferred.
- the light control particles obtained by the production method of the present invention can be used for various purposes as in the conventional case.
- the light control particles are preferably used as light control particles of a light control material for a light control film.
- the light control film of the present invention comprises a resin matrix formed from a polymer medium that is cured by irradiation with energy rays, a dispersion medium, and light control particles dispersed in a flowable state in the dispersion medium. And a light control layer made of a light control material.
- the light control film of the present invention is preferably formed by sandwiching the light control layer between two transparent conductive substrates.
- examples of the polymer medium that is cured by irradiation with energy rays include polymer compositions that are cured by energy rays such as ultraviolet rays, visible rays, and electron beams.
- examples of the polymer composition include a polymer composition containing a polymer compound having a substituent having an ethylenically unsaturated bond and a photopolymerization initiator.
- a silicone resin, an acrylic resin, a polyester resin, or the like is preferable from the viewpoints of ease of synthesis, light control performance, durability, and the like.
- These resins may further have a substituent.
- the substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, and a hexyl group.
- an alkyl group such as a cyclohexyl group
- an aryl group such as a phenyl group and a naphthyl group are preferable from the viewpoints of light control performance and durability.
- a photopolymerization initiator that activates radical polymerization when exposed to energy rays can be used.
- the dispersion medium in the light-adjusting suspension one that is phase-separated from the polymer medium and a resin matrix that is a cured product thereof is used.
- the light adjusting particles serve to disperse the light adjusting particles in a flowable state, and are selectively attached and coated on the light adjusting particles so that the light adjusting particles are phase-separated during phase separation from the polymer medium.
- Liquid that acts to move to the droplet phase has no electrical conductivity, has no affinity with the polymer medium, and has a refractive index approximate to that of the resin matrix formed from the polymer medium when used as a light control film A copolymer is used.
- a (meth) acrylic acid ester oligomer having a fluoro group and / or a hydroxyl group is preferred, and a (meth) acrylic acid ester oligomer having a fluoro group and a hydroxyl group is more preferred.
- one monomer unit of either a fluoro group or a hydroxyl group has an affinity for the light control particle, and the remaining monomer unit is a droplet of the light control suspension in a polymer medium. Since it works to maintain stability, the light adjusting particles are easily dispersed in the light adjusting suspension, and the light adjusting particles are easily guided into the phase-separated droplets during the phase separation.
- Examples of the (meth) acrylic acid ester oligomer having such a fluoro group and / or hydroxyl group include 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, acrylic acid 3 , 5,5-trimethylhexyl / 2-hydroxypropyl acrylate / fumaric acid copolymer, butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl acrylate / acrylic Butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, acrylic acid 1H, 1H, 5H-octafluoropentyl / butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, acrylic acid 1H, 1H, 2H, 2H-hepta Decafluorodecyl / butyl acrylate / acrylic acid 2-hydroxy E
- the light control suspension in the present invention preferably contains 1 to 15% by weight of light control particles, more preferably 2 to 10% by weight, based on the total weight of the light control suspension.
- the dispersion medium is preferably contained in an amount of 30 to 99% by mass, more preferably 50 to 96% by mass, based on the total mass of the light control suspension.
- the light-modulating material preferably contains 1 to 100 parts by weight, more preferably 4 to 70 parts by weight, and more preferably 6 to 60 parts by weight of the light control suspension with respect to 100 parts by weight of the polymer medium. More preferably, it is contained in an amount of 8 to 50 parts by mass.
- the light control material is applied on a transparent conductive substrate, and the polymer medium is irradiated with energy rays to form a light control layer. It can manufacture by sticking a transparent conductive substrate.
- a light adjustment suspension is prepared as follows. A liquid in which the light control particles are dispersed in a solvent and a dispersion medium of the light control suspension are mixed, and the solvent is distilled off with a rotary evaporator or the like.
- the light control suspension and the polymer medium are mixed to obtain a mixed liquid (light control material) in which the light control suspension is dispersed in a droplet state in the polymer medium.
- This mixed solution is applied on a transparent conductive substrate with a certain thickness, and after removing the solvent by drying as necessary, the polymer medium is cured by irradiating energy rays using a metal halide lamp, high-pressure mercury lamp, etc. Let As a result, a film is obtained in which the liquid light control suspension is dispersed in the form of droplets in the cured resin matrix containing the polymer medium. At this time, the light transmittance of the film can be adjusted by variously changing the mixing ratio of the polymer medium and the light control suspension.
- a light control film can be obtained by bringing another transparent conductive substrate into close contact with the light control layer thus formed.
- Another transparent conductive substrate may be brought into close contact with the light control layer before the energy ray irradiation, or may be brought into close contact with the light control layer during the energy ray irradiation.
- a light control layer may be formed on each surface of the two transparent conductive substrates, and the light control layers may be laminated so that the light control layers are in close contact with each other.
- the thickness of the light control layer is preferably 5 to 1,000 ⁇ m, and more preferably 20 to 100 ⁇ m.
- the light control suspension and the polymer medium are mixed with a homogenizer, an ultrasonic homogenizer, etc.
- a method of finely dispersing the prepared suspension, a phase separation method by polymerization of polymer compound components in the polymer medium, a phase separation method by solvent volatilization when the polymer medium contains a solvent, a phase separation method by temperature, etc. can be used.
- a coating means such as a bar coater, an applicator, a doctor blade, a roll coater, a die coater, and a comma coater, It can be applied to a substrate such as a conductive substrate.
- a coating you may dilute with a suitable solvent as needed. When a solvent is used, drying is required after coating on the substrate.
- solvent for example, tetrahydrofuran, toluene, heptane, cyclohexane, ethyl acetate, ethanol, methanol, isoamyl acetate, hexyl acetate and the like can be used.
- the transparent conductive substrate for example, a transparent substrate coated with a transparent conductive film such as ITO, SnO 2 or In 2 O 3 can be used.
- the light transmittance of the transparent conductive film is preferably 80% or more, and the thickness of the transparent conductive film is preferably 10 to 5,000 nm.
- the light transmittance can be measured according to the total light transmittance measuring method of JIS K7105.
- a transparent substrate glass, a polymer film, etc. can be used, for example.
- said glass means a substrate transparent to visible light, etc.
- organic materials such as inorganic material glass of various compositions, transparent acrylic resin, polycarbonate resin, etc.
- the used resin glass can also be used.
- the polymer film examples include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride, acrylic resin films, polyether sulfone films, polyarylate films, and polycarbonate films.
- a polyethylene terephthalate film is preferable because it is excellent in transparency and excellent in moldability, adhesiveness, workability, and the like.
- the thickness of the transparent substrate is not particularly limited, but for example, it is preferably 1 to 15 mm in the case of glass, and preferably 10 to 200 ⁇ m in the case of a polymer film.
- the surface resistance value of the transparent conductive substrate is preferably 3 to 600 ⁇ . Further, when producing a light control film by narrowing the distance between the transparent conductive substrates, in order to prevent a short-circuit phenomenon caused by mixing of different substances, the thickness of 200 to 1,000 mm is formed on the transparent conductive film. You may use the board
- a light control film whose light transmittance can be arbitrarily adjusted by forming an electric field can be produced.
- the droplet size (average droplet size) of the light control suspension dispersed in the resin matrix is 0.5 to 0.5 from the viewpoint of preventing aggregation and deposition of the light control particles.
- the thickness is preferably 50 ⁇ m, more preferably 1 to 10 ⁇ m.
- For the average droplet diameter for example, using an optical microscope, take an image such as a photograph from one side of the light control film, and measure multiple droplet diameters (the longest droplet diameter) selected arbitrarily. The average value can be calculated. Further, it is also possible to take a visual field image of the light control film with an optical microscope into a computer as digital data and calculate it using image processing integration software.
- the size of the droplets depends on the concentration of each component constituting the light control suspension, the viscosity of the light control suspension and the polymer medium, and the compatibility of the dispersion medium in the light control suspension with the polymer medium. It is decided by etc.
- the refractive index of the liquid light-adjusting suspension and the refractive index of the polymer medium that cures when irradiated with energy rays are close to each other. It is preferable in terms of improving the degree.
- the power source used is normally AC and can be operated in the frequency range of 10 to 220 volts (effective value) and 30 Hz to 500 kHz.
- the light control film of the present invention includes, for example, indoor and outdoor partitions, window glass / skylights for buildings, various flat display elements used in the electronics industry and video equipment, various instrument panels, and existing liquid crystal display elements. Suitable for applications such as light shutters, various indoor / outdoor advertisements and signboards, window glass for aircraft / railway vehicles / ships, window glass / back mirror / sunroof for automobiles, glasses, sunglasses, sun visors, etc. Can be used.
- the light control film of the present invention may be sandwiched between two base materials or used. It may be used by pasting it on one side.
- said base material glass, a polymer film, etc. can be used similarly to the said transparent substrate, for example.
- Example 1 From iodine (JIS reagent special grade, Wako Pure Chemical Industries, Ltd.) and isopentyl acetate (reagent special grade, Wako Pure Chemical Industries, Ltd.), an 8.47 mass% iodine isopentyl acetate solution, and cellulose nitrate 1/4 LIG
- An isopentyl acetate solution of 20.0 mass% cellulose nitrate was prepared from (trade name: manufactured by Bergerac NC) and isopentyl acetate.
- Calcium iodide hydrate (chemical use, manufactured by Wako Pure Chemical Industries, Ltd.) was dried by heating, dehydrated and dissolved in isopentyl acetate to prepare a 20.88 mass% calcium iodide solution.
- a 300 ml four-necked flask was equipped with a stirrer and a condenser, and 65.55 g of iodine solution and 82.93 g of cellulose nitrate solution were added, and the flask was heated at a water bath temperature of 35 to 40 ° C. After the temperature of the contents of the flask reached 35 to 40 ° C., 7.41 g of dehydrated methanol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and purified water (manufactured by Wako Pure Chemical Industries, Ltd.) were added to 0. 525 g was added and stirred.
- dehydrated methanol special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.
- purified water manufactured by Wako Pure Chemical Industries, Ltd.
- the water ratio (%) in the cellulose nitrate solution was measured using Hiranuma Sangyo Co., Ltd. Hiranuma moisture measuring device AQ-7 (generating liquid: Hydranal Aqualite RS, counter electrode liquid: Aqualite CN).
- the amount of water in the cellulose nitrate solution was 0.697 g from the mass of the added solution.
- the amount of water present in the reaction system was 1.222 g if it was contained in cellulose nitrate and purified water added.
- calcium iodide contains 0 to 1% by mass of moisture after drying after heating and drying and is dehydrated. However, moisture content is considered because accurate measurement is difficult. Not done.
- the amount of methanol was 59.2 parts by mass when the total mass of 12.51 g of (A), (B) and (C) was 100 parts by mass, and the water content was 9.77 parts by mass.
- the obtained light control particles had a particle diameter of 139 nm determined by particle size distribution measurement, a major axis of 259 nm and an aspect ratio of 4.1 by SEM observation.
- the supernatant was removed by inclining, and the precipitate remaining at the bottom was added with 5 times the mass of the precipitate, isopentyl acetate to disperse the precipitate with ultrasound, The mass of the whole liquid was measured.
- the dispersed liquid was weighed on a 1 g metal plate, dried at 120 ° C. for 1 hour, then weighed again to determine the non-volatile content ratio%. From the nonvolatile content ratio and the mass of the entire liquid, the total nonvolatile content, that is, the precipitation yield of 4.15 g was determined.
- Example 2 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.300 g and the added cellulose nitrate solution was 83.05 g. The amount of water in the cellulose nitrate solution was 0.673 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 0.973 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.78 parts by mass.
- the obtained light control particles had a particle diameter of 147 nm determined by particle size distribution measurement, a major axis of 307 nm, an aspect ratio of 4.5, and a precipitation yield of 4.74 g as observed by SEM.
- Example 3 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.375 g and the added cellulose nitrate solution was 82.54 g. The amount of water in the cellulose nitrate solution was 0.669 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.044 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 8.34 parts by mass.
- the obtained light control particles had a particle diameter of 162 nm determined by particle size distribution measurement, a major axis of 400 nm, an aspect ratio of 5.5, and a precipitation yield of 5.76 g as observed by SEM.
- Example 4 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.375 g and the added cellulose nitrate solution was 82.89 g. The amount of water in the cellulose nitrate solution was 0.671 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.046 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.37 parts by mass.
- the obtained light control particles had a particle diameter of 162 nm determined by particle size distribution measurement, a major axis of 400 nm, an aspect ratio of 5.2, and a precipitation yield of 5.63 g as observed by SEM.
- Example 5 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.450 g and the added cellulose nitrate solution was 82.25 g. The amount of water in the cellulose nitrate solution was 0.666 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.116 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.92 parts by mass.
- the obtained light control particles had a particle diameter of 200 nm determined by particle size distribution measurement, a major axis of 594 nm, an aspect ratio of 6.3, and a precipitation yield of 7.41 g by SEM observation.
- Example 6 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.325 g and the added cellulose nitrate solution was 83.13 g. The amount of water in the cellulose nitrate solution was 0.798 g (water ratio 0.96% by mass), and the amount of water present in the reaction system was 1.123 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.98 parts by mass.
- the obtained light control particles had a particle diameter of 189 nm determined by particle size distribution measurement, a major axis of 384 nm, an aspect ratio of 5.3, and a precipitation yield of 6.62 g by SEM observation.
- Example 7 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.525 g and the added cellulose nitrate solution was 82.77 g. The amount of water in the cellulose nitrate solution was 0.6709 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.195 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 9.56 parts by mass.
- the obtained light control particles had a particle diameter of 231 nm determined by particle size distribution measurement, a major axis of 581 nm, an aspect ratio of 6.9, and a precipitation yield of 7.70 g as observed by SEM.
- Example 8 Calcium iodide hydrate was dried by heating and dehydrated and dissolved in isopentyl acetate and methanol to prepare a 20.88% calcium iodide solution. At this time, the mass ratio of isopentyl acetate and methanol is 2.0: 3.0. A 300 ml four-necked flask was equipped with a stirrer and a condenser, and 65.55 g of iodine solution and 82.71 g of cellulose nitrate solution were added and stirred.
- the flask was heated at a water bath temperature of 42 to 44 ° C., and after the contents reached 42 to 44 ° C., purified water was not added, 15.6 g of calcium iodide solution was added, and then pyrazine-2,5-dicarboxylic acid was added. 3.70 g was added. The mixture was stirred for 2 hours at a water bath temperature of 42 to 44 ° C. and then allowed to cool.
- the amount of water in the cellulose nitrate solution was 0.695 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 0.695 g.
- Methanol amount was 59.2 parts by mass with a total mass of 12.51 g of (A), (B) and (C) as 100 parts by mass, and the water content was 5.55 parts by mass.
- the obtained light control particles had a particle diameter of 126 nm determined by particle size distribution measurement, a major axis of 173 nm and an aspect ratio of 2.3 by SEM observation.
- Example 9 Light adjusting particles were produced in the same manner as in Example 8 with 0.325 g of purified water added and 83.05 g of the added cellulose nitrate solution.
- the amount of water in the cellulose nitrate solution was 0.698 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.023 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.17 parts by mass.
- the obtained light control particles had a particle diameter of 155 nm determined by particle size distribution measurement, a major axis of 335 nm, an aspect ratio of 4.6, and a precipitation yield of 6.37 g by SEM observation.
- Example 10 Light adjustment particles were produced in the same manner as in Example 8 except that the amount of purified water added was 0.375 g and the added cellulose nitrate solution was 82.78 g. The amount of water in the cellulose nitrate solution was 0.695 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.070 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.56 parts by mass.
- the obtained light control particles had a particle diameter of 169 nm determined by particle size distribution measurement, a major axis of 348 nm, an aspect ratio of 4.8, and a precipitation yield of 6.46 g as observed by SEM.
- Example 11 Light adjustment particles were produced in the same manner as in Example 8 with 0.375 g of purified water added and 82.83 g of the added cellulose nitrate solution.
- the amount of water in the cellulose nitrate solution was 0.696 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.071 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.56 parts by mass.
- the obtained light control particles had a particle diameter of 167 nm determined by particle size distribution measurement, a major axis of 343 nm, an aspect ratio of 4.7, and a precipitation yield of 6.49 g as observed by SEM.
- Example 12 Light adjustment particles were produced in the same manner as in Example 8 with 0.375 g of purified water added and 83.18 g of the added cellulose nitrate solution.
- the amount of water in the cellulose nitrate solution was 0.699 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.074 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.58 parts by mass.
- the obtained light control particles had a particle diameter of 177 nm determined by particle size distribution measurement, a major axis of 402 nm, an aspect ratio of 5.1, and a precipitation yield of 6.26 g as observed by SEM.
- Example 13 Light adjusting particles were produced in the same manner as in Example 8 with 0.375 g of purified water added and 83.28 g of the added cellulose nitrate solution.
- the amount of water in the cellulose nitrate solution was 0.700 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.075 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 8.59 parts by mass.
- the obtained light control particles had a particle diameter of 178 nm determined by particle size distribution measurement, a major axis of 409 nm, an aspect ratio of 5.2, and a precipitation yield of 6.55 g by SEM observation.
- Example 14 Light adjustment particles were produced in the same manner as in Example 8 except that the amount of purified water added was 0.475 g and the added cellulose nitrate solution was 82.59 g. The amount of water in the cellulose nitrate solution was 0.694 g (water ratio 0.84% by mass), and the amount of water present in the reaction system was 1.169 g.
- the amount of methanol was 59.2 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 9.34 parts by mass.
- the obtained light control particles had a particle diameter of 213 nm determined by particle size distribution measurement, a major axis of 505 nm, an aspect ratio of 5.6, and a precipitation yield of 7.45 g by SEM observation.
- Example 15 The amount of purified water added was 0.375 g, the added cellulose nitrate solution was 82.63 g, and dehydrated methanol was 9.88 g. The amount of water in the cellulose nitrate solution was 0.669 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.044 g.
- the amount of methanol was 79.0 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.35 parts by mass.
- the obtained light control particles had a particle diameter of 159 nm determined by particle size distribution measurement, a major axis of 382 nm, an aspect ratio of 5.0, and a precipitation yield of 5.59 g as observed by SEM.
- Example 16 The amount of purified water added was 0.450 g, the added cellulose nitrate solution was 82.59 g, and dehydrated methanol was 9.88 g. The amount of water in the cellulose nitrate solution was 0.669 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.119 g.
- the amount of methanol was 79.0 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.95 parts by mass.
- the obtained light control particles had a particle diameter of 183 nm determined by particle size distribution measurement, a major axis of 462 nm, an aspect ratio of 5.3, and a precipitation yield of 6.78 g as observed by SEM.
- Example 17 Light adjustment particles were produced in the same manner as in Example 1 except that the amount of purified water added was 0.300 g, the added cellulose nitrate solution was 83.21 g, and dehydrated methanol was 12.35 g. The amount of water in the cellulose nitrate solution was 0.649 g (water ratio 0.78% by mass), and the amount of water present in the reaction system was 0.949 g.
- the amount of methanol was 98.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.59 parts by mass.
- the obtained light control particles had a particle diameter of 139 nm determined by particle size distribution measurement, a major axis of 242 nm, an aspect ratio of 3.1, and a precipitation yield of 5.38 g by SEM observation.
- Example 18 The amount of purified water added was 0.375 g, the added cellulose nitrate solution was 83.25 g, and dehydrated methanol was 12.35 g. The amount of water in the cellulose nitrate solution was 0.649 g (water ratio 0.78% by mass), and the amount of water present in the reaction system was 1.024 g.
- the amount of methanol was 98.7 parts by mass and the amount of water was 8.19 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C).
- the obtained light control particles had a particle diameter of 149 nm determined by particle size distribution measurement, a major axis of 232 nm, an aspect ratio of 3.0, and a precipitation yield of 5.47 g by SEM observation.
- Example 19 The amount of purified water added was 0.450 g, the added cellulose nitrate solution was 82.89 g, and dehydrated methanol was 12.35 g. The amount of water in the cellulose nitrate solution was 0.647 g (water ratio 0.78% by mass), and the amount of water present in the reaction system was 1.097 g.
- the amount of methanol was 98.7 parts by mass and the amount of water was 8.77 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C).
- the obtained light control particles had a particle diameter of 174 nm determined by particle size distribution measurement, a major axis of 351 nm, an aspect ratio of 4.1, and a precipitation yield of 6.79 g as observed by SEM.
- Example 20 The amount of purified water added was 0.525 g, the added cellulose nitrate solution was 82.96 g, and dehydrated methanol was 12.35 g. The amount of water in the cellulose nitrate solution was 0.672 g (water ratio 0.81% by mass), and the amount of water present in the reaction system was 1.197 g.
- the amount of methanol was 98.7 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C), and the water content was 9.57 parts by mass.
- the obtained light control particles had a particle size of 213 nm determined by particle size distribution measurement, a major axis of 607 nm, an aspect ratio of 5.6, and a precipitation yield of 6.98 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 5.36 parts by mass.
- the obtained light control particles had a particle diameter of 86 nm determined by particle size distribution measurement, a major axis of 114 nm, an aspect ratio of 1.6, and a precipitation yield of 1.73 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 7.56 parts by mass.
- the obtained light control particles had a particle diameter of 144 nm determined by particle size distribution measurement, a major axis of 308 nm, an aspect ratio of 4.0, and a precipitation yield of 3.76 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.81 parts by mass.
- the obtained light control particles had a particle size of 173 nm determined by particle size distribution measurement, a major axis of 397 nm, an aspect ratio of 5.1, and a precipitation yield of 5.96 g as observed by SEM.
- the amount of methanol was 19.7 parts by mass and the amount of water was 7.82 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C).
- the obtained light control particles had a particle diameter of 166 nm determined by particle size distribution measurement, a major axis of 370 nm, an aspect ratio of 5.3, and a precipitation yield of 4.93 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.83 parts by mass.
- the obtained light control particles had a particle diameter of 169 nm determined by particle size distribution measurement, a major axis of 378 nm, an aspect ratio of 5.2, and a precipitation yield of 4.98 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.84 parts by mass.
- the obtained light control particles had a particle diameter of 170 nm determined by particle size distribution measurement, a major axis of 401 nm, an aspect ratio of 4.9, and a precipitation yield of 4.35 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.85 parts by mass.
- the obtained light control particles had a particle diameter of 161 nm determined by particle size distribution measurement, a major axis of 376 nm, an aspect ratio of 5.4, and a precipitation yield of 4.13 g as observed by SEM.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.96 parts by mass.
- the obtained light control particles had a particle diameter of 180 nm obtained by particle size distribution measurement, a major axis of 401 nm, an aspect ratio of 4.7, and a precipitation yield of 7.09 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.00 parts by mass.
- the obtained light control particles had a particle diameter of 165 nm obtained by particle size distribution measurement, a major axis of 366 nm, an aspect ratio of 4.1, and a precipitation yield of 6.26 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.17 parts by mass.
- the obtained light control particles had a particle diameter of 187 nm determined by particle size distribution measurement, a major axis of 436 nm, an aspect ratio of 5.3, and a precipitation yield of 7.04 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.17 parts by mass.
- the obtained light control particles had a particle diameter of 183 nm determined by particle size distribution measurement, a major axis of 423 nm, an aspect ratio of 4.7, and a precipitation yield of 6.92 g as observed by SEM.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.15 parts by mass.
- the obtained light control particles had a particle diameter of 190 nm determined by particle size distribution measurement, a major axis of 476 nm, an aspect ratio of 5.0, and a precipitation yield of 7.35 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.15 parts by mass.
- the obtained light control particles had a particle size of 173 nm determined by particle size distribution measurement, a major axis of 412 nm, an aspect ratio of 5.4, and a precipitation yield of 6.60 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C), and the water content was 8.14 parts by mass.
- the obtained light control particles had a particle diameter of 185 nm determined by particle size distribution measurement, a major axis of 454 nm, an aspect ratio of 4.8, and a precipitation yield of 7.21 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.18 parts by mass.
- the obtained light control particles had a particle diameter of 170 nm determined by particle size distribution measurement, a major axis of 390 nm, an aspect ratio of 5.1, and a precipitation yield of 6.37 g by SEM observation.
- the amount of methanol was 19.7 parts by mass and the amount of water was 8.23 parts by mass with respect to 100 parts by mass in total of (A), (B) and (C).
- the obtained light control particles had a particle diameter of 190 nm obtained by particle size distribution measurement, a major axis of 462 nm, an aspect ratio of 5.6, and a precipitation yield of 7.15 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.38 parts by mass.
- the obtained light control particles had a particle size of 198 nm determined by particle size distribution measurement, a major axis of 455 nm, an aspect ratio of 5.6, and a precipitation yield of 6.76 g by SEM observation.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 8.98 parts by mass.
- the obtained light control particles had a particle diameter of 252 nm determined by particle size distribution measurement, a major axis of 645 nm, an aspect ratio of 7.1, and a precipitation yield of 7.61 g as observed by SEM.
- the amount of methanol was 19.7 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 9.58 parts by mass.
- the obtained light control particles had a particle diameter of 260 nm obtained by particle size distribution measurement, a major axis of 689 nm, an aspect ratio of 5.5, and a precipitation yield of 7.50 g as observed by SEM.
- the amount of methanol was 39.5 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.83 parts by mass.
- the obtained light control particles had a particle diameter of 181 nm determined by particle size distribution measurement, a major axis of 466 nm, an aspect ratio of 5.4, and a precipitation yield of 6.64 g by SEM observation.
- the amount of methanol was 39.5 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 7.9 parts by mass.
- the obtained light control particles had a particle diameter of 184 nm determined by particle size distribution measurement, a major axis of 409 nm, an aspect ratio of 4.8, and a precipitation yield of 6.80 g by SEM observation.
- the amount of methanol was 39.5 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the water content was 9.02 parts by mass.
- the obtained light control particles had a particle size of 261 nm determined by particle size distribution measurement, a major axis of 851 nm, an aspect ratio of 7.3, and a precipitation yield of 7.48 g as observed by SEM.
- the amount of methanol was 197.4 parts by mass with respect to a total of 100 parts by mass of (A), (B) and (C), and the moisture content was 8.201 parts by mass.
- the obtained light control particles had a particle diameter of 300 nm determined by particle size distribution measurement, a major axis of 386 nm, an aspect ratio of 2.4, and a precipitation yield of 4.05 g as observed by SEM.
- Table 1 shows the results of Examples 1 to 20 and Comparative Examples 1 to 23. As can be seen from Table 1, the use of an appropriate amount of methanol within the scope of the present invention can reduce the effect of moisture on the resulting particle size.
- particles having a desired size can be obtained. ⁇ 625 nm is obtained with better yield than when methanol is used in amounts outside the scope of the present invention.
- the influence of moisture is reduced and reproducibility is good in the granulation step of the method of manufacturing light adjusting particles.
- a method for producing a light control particle in order to efficiently obtain light adjusting particles having an optimal particle size and shape as a light modulating material, the influence of moisture is reduced and reproducibility is good in the granulation step of the method of manufacturing light adjusting particles.
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Abstract
Description
この調光フィルムは、光調整粒子を分散した光調整懸濁液の微細な液滴が、紫外線照射によって硬化した樹脂マトリックス中に分散した調光材料をフィルム状とした調光層を用いたフィルムである。この調光フィルム中で光調整粒子は、電界を印加していない状態では、ブラウン運動により光を吸収、散乱又は反射するため、フィルムへの入射光は透過できない。電界を印加した場合、光調整粒子の分極により、電界につれて平行な方向に配列するため、フィルムに入射した光を透過させはじめる。このように、光調整粒子の電界への応答により、光の透過量を調整している(例えば、特許文献1参照)。
分散媒と、該分散媒中に流動可能な状態で分散した光調整粒子と、を有する光調整懸濁液、を含有する調光材料に用いることが可能な光調整粒子の製造方法であって、
(A)元素状分子ヨウ素、(B)アルカリ土類金属ヨウ化物、(C)複素環式化合物とを媒体中で混合して造粒する工程において、前記(A)、(B)及び(C)の合計100質量部に対して50質量部以上110質量部以下のメタノールを共存させ、反応させることを特徴とする光調整粒子の製造方法。
分散媒と、該分散媒中に流動可能な状態で分散した光調整粒子と、を有する光調整懸濁液、を含む調光材料からなる調光層を有する調光フィルムにおいて、
前記光調整粒子が上記(1)~(3)のいずれか一つに記載の光調整粒子の製造方法で得られたことを特徴とする調光フィルム。
分散媒と、該分散媒中に流動可能な状態で分散した光調整粒子と、を有する光調整懸濁液、を含有する調光材料に用いることが可能な光調整粒子の製造方法であって、
(A)元素状分子ヨウ素、(B)アルカリ土類金属ヨウ化物、(C)複素環式化合物とを媒体中で混合して造粒する工程において、前記(A)、(B)及び(C)の合計100質量部に対して50質量部以上110質量部以下のメタノールを共存させ、反応させることを特徴とする。
また、調光材料は、フィルム状の調光層として用いられ、該調光層を2枚の透明導電性基板間等に挟んで調光フィルムを形成することが可能である。
また、用いる(A)元素状分子ヨウ素は、特に制限がないが、粉末状、もしくは球状微粒子等のように媒体に溶解しやすいものが好ましい。
上記式(1)中、好ましいのはR1、R2は、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、t-ブチル基等であり、より具体的には、ピラジン-2,5-ジカルボン酸等が挙げられ、これらは水和物として用いることも可能である。
一般にはセルロースを硝酸エステル化する工程でニトロ基の含有量により分類されているが、いずれのものも、本発明の光調整粒子の製造方法に用いられる媒体としての有機溶媒に溶解する限り、用いることができる。
従って、反応系内に投入する場合は固体のままでもよいし、一旦有機溶媒に溶解して投入してもよい。具体的にはベルジュラックNC社製LIG1/8、LIG1/4、LIG1/2A、LIG1/2、HIG1/16、HIG1/8、HIG1/4、HIG1/2A、HIG1/2、HIG1、HIG2、HIG5、HIG7、HIG20、ノーベルエンタープライズ社製DHX1-2,DHX3-5、DHX4-6、DHX5-10、DHX8-13、DHX11-16、DHX30-50、DHX40-70、DHL25-45、DHL120-170、DLX3-5、DLX5-8、DLX8-13、DLX30-50、などを挙げることができる。
特にアスペクト比の大きな光調整粒子、具体的にはアスペクト比3~8、長径225~625nm、且つ粒度分布測定により求められる粒子径135~220nmの光調整粒子を得るためには、上記(A)、(B)、(C)の合計100質量部に対して90~150質量部が好ましく、100~145質量部がより好ましく、105~140質量部がさらに好ましい。
例えば、フルオロ基及び/又は水酸基を有する(メタ)アクリル酸エステルオリゴマーが好ましく、フルオロ基及び水酸基を有する(メタ)アクリル酸エステルオリゴマーがより好ましい。このような共重合体を使用すると、フルオロ基、水酸基のどちらか1つのモノマー単位は光調整粒子に親和性があり、残りのモノマー単位は高分子媒体中で光調整懸濁液が液滴として安定に維持するために働くことから、光調整懸濁液内に光調整粒子が分散しやすく、相分離の際に光調整粒子が相分離される液滴内に誘導されやすい。
このようにして形成された調光層の上に他の透明導電性基板を密着させることにより、調光フィルムが得られる。他の透明導電性基板は、エネルギー線照射前に調光層に密着させてもよいし、エネルギー線照射時に調光層に密着させてもよい。また、2枚の透明導電性基板の各面に調光層を形成し、それを調光層同士が密着するようにして積層してもよい。調光層の厚みは、5~1,000μmが好ましく、20~100μmがより好ましい。
なお、光透過率はJIS K7105の全光線透過率の測定法に準拠して測定することができる。また、透明基板としては、例えば、ガラス、高分子フィルム等を使用することができる。
平均液滴径は、例えば、光学顕微鏡を用いて、調光フィルムの一方の面方向から写真等の画像を撮影し、任意に選択した複数の液滴直径(液滴の最長の径)を測定し、その平均値として算出することができる。また、上記調光フィルムの光学顕微鏡での視野画像をデジタルデータとしてコンピュータに取り込み、画像処理インテグレーションソフトウェアを使用し算出することも可能である。液滴の大きさは、光調整懸濁液を構成している各成分の濃度、光調整懸濁液及び高分子媒体の粘度、光調整懸濁液中の分散媒の高分子媒体に対する相溶性等により決められる。
ヨウ素(JIS試薬特級、和光純薬工業(株)製)と酢酸イソペンチル(試薬特級、和光純薬工業(株)製)から8.47質量%ヨウ素の酢酸イソペンチル溶液を、また硝酸セルロース1/4LIG(商品名:ベルジュラックNC社製)と酢酸イソペンチルから20.0質量%硝酸セルロースの酢酸イソペンチル溶液を調製した。
ヨウ化カルシウム水和物(化学用、和光純薬工業(株)製)を加熱乾燥して無水化して酢酸イソペンチルに溶解させ、20.88質量%ヨウ化カルシウム溶液を調整した。300mlの四口フラスコに撹拌機と冷却管を備え、ヨウ素溶液を65.55g、硝酸セルロース溶液を82.93g、を加え水浴温度を35~40℃としてフラスコを加熱した。フラスコ内容物の温度が35~40℃となった後、脱水メタノール(試薬特級、和光純薬工業(株)製)を7.41g、精製水(和光純薬工業(株)製)を0.525g加えて撹拌した。
ヨウ化カルシウム溶液を15.6g、次いでピラジン-2,5-ジカルボン酸(日化テクノサービス(株)製)を3.70g加えた。水浴温度を42~44℃として4時間撹拌した後、放冷した。
なお、本実施例において、ヨウ化カルシウムについては加熱乾燥して無水化した後、吸湿性が強いため乾燥後0~1質量%の水分を含むが、正確な測定が困難なため水分量は考慮していない。
この分散した液を1g金属プレートに秤量し、120℃1時間で乾燥後、再び質量を測定し、不揮発分比%を求めた。この不揮発分比と液全体の質量から全不揮発分量、すなわち沈殿収量4.15gを求めた。
加えた精製水の量を0.300g、加えた硝酸セルロース溶液を83.05gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.673g(水分比0.81質量%)、反応系内に存在する水分量は0.973gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.54gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.669g(水分比0.81質量%)、反応系内に存在する水分量は1.044gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.89gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.671g(水分比0.81質量%)、反応系内に存在する水分量は1.046gであった。
加えた精製水の量を0.450g、加えた硝酸セルロース溶液を82.25gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.666g(水分比0.81質量%)、反応系内に存在する水分量は1.116gであった。
加えた精製水の量を0.325g、加えた硝酸セルロース溶液を83.13gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.798g(水分比0.96質量%)、反応系内に存在する水分量は1.123gであった。
加えた精製水の量を0.525g、加えた硝酸セルロース溶液を82.77gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.6709g(水分比0.81質量%)、反応系内に存在する水分量は1.195gであった。
ヨウ化カルシウム水和物を加熱乾燥して無水化して酢酸イソペンチルとメタノールに溶解させ、20.88%ヨウ化カルシウム溶液を調整した。このとき、酢酸イソペンチルとメタノールの質量比は2.0:3.0である。300mlの四口フラスコに撹拌機と冷却管を備え、ヨウ素溶液を65.55g、硝酸セルロース溶液を82.71g、加えて撹拌した。
水浴温度を42~44℃としてフラスコを加熱し、内容物が42~44℃となった後、精製水は加えず、ヨウ化カルシウム溶液を15.6g、次いでピラジン-2,5-ジカルボン酸を3.70g加えた。水浴温度を42~44℃として2時間撹拌した後、放冷した。硝酸セルロース溶液中の水分量は0.695g(水分比0.84質量%)、反応系内に存在する水分量は0.695gであった。
加えた精製水の量を0.325g、加えた硝酸セルロース溶液を83.05gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.698g(水分比0.84質量%)、反応系内に存在する水分量は1.023gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.78gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.695g(水分比0.84質量%)、反応系内に存在する水分量は1.070gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.83gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.696g(水分比0.84質量%)、反応系内に存在する水分量は1.071gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.18gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.699g(水分比0.84質量%)、反応系内に存在する水分量は1.074gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.28gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.700g(水分比0.84質量%)、反応系内に存在する水分量は1.075gであった。
加えた精製水の量を0.475g、加えた硝酸セルロース溶液を82.59gとして実施例8と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.694g(水分比0.84質量%)、反応系内に存在する水分量は1.169gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.63g、脱水メタノールを9.88gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.669g(水分比0.81質量%)、反応系内に存在する水分量は1.044gであった。
加えた精製水の量を0.450g、加えた硝酸セルロース溶液を82.59g、脱水メタノールを9.88gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.669g(水分比0.81質量%)、反応系内に存在する水分量は1.119gであった。
加えた精製水の量を0.300g、加えた硝酸セルロース溶液を83.21g、脱水メタノールを12.35gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.649g(水分比0.78質量%)、反応系内に存在する水分量は0.949gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.25g、脱水メタノールを12.35gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.649g(水分比0.78質量%)、反応系内に存在する水分量は1.024gであった。
加えた精製水の量を0.450g、加えた硝酸セルロース溶液を82.89g、脱水メタノールを12.35gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.647g(水分比0.78質量%)、反応系内に存在する水分量は1.097gであった。
加えた精製水の量を0.525g、加えた硝酸セルロース溶液を82.96g、脱水メタノールを12.35gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.672g(水分比0.81質量%)、反応系内に存在する水分量は1.197gであった。
精製水を加えずに、また、加えた硝酸セルロース溶液を82.78g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.671g(水分比0.81質量%)、反応系内に存在する水分量は0.671gであった。
加えた精製水の量を0.300g、加えた硝酸セルロース溶液を82.78g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.646g(水分比0.78質量%)、反応系内に存在する水分量は0.946gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.48g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.602g(水分比0.73質量%)、反応系内に存在する水分量は0.977gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.71g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.604g(水分比0.73質量%)、反応系内に存在する水分量は0.979gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.85g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.605g(水分比0.73質量%)、反応系内に存在する水分量は0.980gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.89g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.605g(水分比0.73質量%)、反応系内に存在する水分量は0.980gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.10g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.607g(水分比0.73質量%)、反応系内に存在する水分量は0.982gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.84g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.621g(水分比0.75質量%)、反応系内に存在する水分量は0.996gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.31g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.626g(水分比0.76質量%)、反応系内に存在する水分量は1.001gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.94g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.647g(水分比0.78質量%)、反応系内に存在する水分量は1.022gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.96g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.647g(水分比0.78質量%)、反応系内に存在する水分量は1.022gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.69g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.645g(水分比0.78質量%)、反応系内に存在する水分量は1.020gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.58g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.644g(水分比0.78質量%)、反応系内に存在する水分量は1.019gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.47g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.643g(水分比0.78質量%)、反応系内に存在する水分量は1.018gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.14g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.648g(水分比0.78質量%)、反応系内に存在する水分量は1.023gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.85g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.654g(水分比0.78質量%)、反応系内に存在する水分量は1.029gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.05g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.673g(水分比0.81質量%)、反応系内に存在する水分量は1.048gであった。
加えた精製水の量を0.450g、加えた硝酸セルロース溶液を83.17g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.674g(水分比0.81質量%)、反応系内に存在する水分量は1.124gであった。
加えた精製水の量を0.525g、加えた硝酸セルロース溶液を83.09g、脱水メタノールを2.47gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.673g(水分比0.81質量%)、反応系内に存在する水分量は1.198gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を82.88g、脱水メタノールを4.94gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.603g(水分比0.73質量%)、反応系内に存在する水分量は0.980gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.19g、脱水メタノールを4.94gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.624g(水分比0.75質量%)、反応系内に存在する水分量は0.999gであった。
加えた精製水の量を0.525g、加えた硝酸セルロース溶液を82.60g、脱水メタノールを4.94gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.605g(水分比0.73質量%)、反応系内に存在する水分量は1.128gであった。
加えた精製水の量を0.375g、加えた硝酸セルロース溶液を83.46g、脱水メタノールを24.69gとして実施例1と同様にして、光調整粒子を製造した。硝酸セルロース溶液中の水分量は0.651g(水分比0.78質量%)、反応系内に存在する水分量は1.026gであった。
Claims (5)
- エネルギー線を照射することにより硬化する高分子媒体から形成された樹脂マトリックス及び、
分散媒と、該分散媒中に流動可能な状態で分散した光調整粒子と、を有する光調整懸濁液、を含有する調光材料に用いることが可能な光調整粒子の製造方法であって、
(A)元素状分子ヨウ素、(B)アルカリ土類金属ヨウ化物、(C)複素環式化合物とを媒体中で混合して造粒する工程において、前記(A)、(B)及び(C)の合計100質量部に対して50質量部以上110質量部以下のメタノールを共存させ、反応させることを特徴とする光調整粒子の製造方法。 - 前記(B)アルカリ土類金属ヨウ化物が、ヨウ化カルシウムであることを特徴とする請求項1に記載の光調整粒子の製造方法。
- 前記造粒工程において、硝酸セルロースを共存させることを特徴とする請求項1~3のいずれか一項に記載の光調整粒子の製造方法。
- エネルギー線を照射することにより硬化する高分子媒体から形成された樹脂マトリックス及び、
分散媒と、該分散媒中に流動可能な状態で分散した光調整粒子と、を有する光調整懸濁液、を含む調光材料からなる調光層を有する調光フィルムにおいて、
前記光調整粒子が請求項1~3のいずれか一項に記載の光調整粒子の製造方法で得られたことを特徴とする調光フィルム。
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JP2010512017A JP5849393B2 (ja) | 2008-05-15 | 2009-05-14 | 光調整粒子の製造方法及び該製造方法で得られた光調整粒子を用いた調光フィルム |
US12/992,360 US8520294B2 (en) | 2008-05-15 | 2009-05-14 | Method for manufacturing light control particles and light control film using light control particles obtained by the method |
EP09746650.2A EP2280305A4 (en) | 2008-05-15 | 2009-05-14 | METHOD FOR MANUFACTURING PHOTOCHROMIC PARTICLES AND INTELLIGENT FILM USING PHOTOCHROMIC PARTICLES MADE THEREBY |
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JP5704075B2 (ja) * | 2010-01-26 | 2015-04-22 | 日立化成株式会社 | 調光材料用(メタ)アクリロイル基含有ポリシロキサン樹脂の製造方法 |
KR20210037719A (ko) * | 2018-11-19 | 2021-04-06 | 저지앙 징이 뉴 머티리얼 테크놀로지 컴퍼니 리미티드 | 무기-유기 하이브리드 코어-쉘 나노로드 및 상기 나노로드를 갖는 광 밸브 |
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JP5913787B2 (ja) * | 2010-02-26 | 2016-04-27 | 株式会社堀場製作所 | 粒度分布測定装置 |
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JP5849393B2 (ja) | 2016-01-27 |
EP2280305A1 (en) | 2011-02-02 |
US8520294B2 (en) | 2013-08-27 |
JP2015163987A (ja) | 2015-09-10 |
US20110063715A1 (en) | 2011-03-17 |
JPWO2009139444A1 (ja) | 2011-09-22 |
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