JP5652033B2 - Manufacturing method of light control suspension, manufacturing method of light control material, and manufacturing method of light control film - Google Patents

Description

  The present invention relates to a method for producing a light control suspension, a method for producing a light control material, a method for manufacturing a light control film, and a light control film group.

  A dimming glass containing a light conditioning suspension was first invented by Edwin. Land, and its form is a liquid between two transparent conductive substrates with a narrow spacing. It has a structure in which a light control suspension in a state is injected (see, for example, Patent Documents 1 and 2). According to Edwin Land's invention, the liquid light-regulating suspension injected between two transparent conductive substrates is light dispersed in the suspension when no electric field is applied. Due to the Brownian motion of the conditioning particles, most of the incident light is reflected, scattered or absorbed by the light conditioning particles and only a small portion is transmitted.

  That is, the degree of transmission, reflection, scattering, or absorption is determined by the shape, properties, concentration, and amount of light energy applied to the light control particles dispersed in the light control suspension. When an electric field is applied to the light control window using the light control glass having the above structure, an electric field is formed in the light control suspension through the transparent conductive substrate, and the light control particles representing the light control function cause polarization, The light adjustment particles are arranged in parallel to each other, and light is transmitted between the light adjustment particles and the light adjustment particles. Finally, the light control glass becomes transparent. However, such an initial light control device is practically agglomeration of light control particles in a light control suspension, sedimentation due to its own weight, hue change due to heat, change in optical density, deterioration due to ultraviolet irradiation, base material However, it was difficult to put it into practical use because it was difficult to maintain the interval and to inject the light adjusting suspension into the interval.

  Robert L. Saxe, FC Lowell, or R. I. Thompson is the initial problem with dimming windows, namely: In addition, there is disclosed a light control window using a light control glass supplemented with aggregation and sedimentation of light adjusting particles, changes in optical density, and the like (see, for example, Patent Documents 3 to 9). In these patents, etc., the density of the light adjusting particles and the suspending agent is determined by a liquid state light adjusting suspension composed of acicular light adjusting crystal particles, a suspension for dispersing crystal particles, a dispersion adjusting agent, a stabilizer, and the like. In order to prevent the light adjustment particles from aggregating by adding a dispersion adjusting agent to improve the dispersibility of the light adjustment particles while preventing the precipitation of the light adjustment particles. Yes. However, these light control glasses, like the conventional light control glass, have a structure in which a liquid light control suspension is enclosed within the interval between two transparent conductive substrates, so that large-scale products can be manufactured. In this case, it is difficult to enclose a uniform suspension within the interval between two transparent conductive substrates, and there is a problem that a lower swelling phenomenon is likely to occur due to a water pressure difference between the upper and lower parts of the product. Also, due to changes in the distance between the substrates due to the external environment, for example, wind pressure, the optical density changes and the hue becomes inhomogeneous, or the periphery for collecting liquid between the transparent conductive substrates. There is a problem that the light-sealing material leaks due to destruction of the sealing material. Further, the response time varies due to deterioration due to ultraviolet rays and a voltage drop between the peripheral portion and the central portion of the transparent conductive substrate.

  As a method for improving this, a liquid light control suspension is mixed with a curable polymer resin solution, and a phase separation method by polymerization, a phase separation method by solvent volatilization, or a phase separation method by temperature is used. A method of manufacturing a light control film has been proposed (see, for example, Patent Document 10). Thus, the transmittance | permeability of the light control film produced can be changed continuously with the alternating voltage applied.

US Pat. No. 1,955,923 US Pat. No. 1,963,496 US Pat. No. 3,756,700 US Pat. No. 4,247,175 U.S. Pat. No. 4,273,422 US Pat. No. 4,407,565 US Pat. No. 4,422,963 US Pat. No. 3,912,365 U.S. Pat. No. 4,078,856 JP 2002-189123 A

  Therefore, when a certain voltage is applied, it is necessary that all the production lots have the same transmittance and no difference in appearance. Here, the transmittance of the light control film varies depending on the concentration of the particles in the light adjusting suspension when the thickness and composition of the film are constant. Therefore, the light adjustment is performed so that the particle concentration is constant. If the suspension can be manufactured, a product with less variation in appearance can be manufactured.

  Here, the light adjustment suspension is prepared from a light adjustment particle dispersion in which light adjustment particles are dispersed in a dispersion medium, and a polymer dispersant that is a liquid medium of the suspension. However, unless the concentration of the light adjusting particles in the light adjusting particle dispersion is accurately known, the particle concentration in the light adjusting suspension will not be constant as a result, resulting in variations in appearance.

  As a method for determining the particle concentration of the light-adjusting particle dispersion, conventionally, the dispersion is heated and dried, and the solid content weight remaining is used as the particle weight in the dispersion to calculate the concentration. However, this method has been found to vary under the influence of the temperature and humidity of the outside air in which the drying box is installed even if the drying conditions are constant. Even when the same drying conditions are used, the solid content rises in the dryer and the measured weight decreases, or temperature unevenness occurs in the dryer. Variations in measured values occur. As a result, the particle concentration in the light adjustment particle dispersion cannot be accurately and accurately obtained, and as a result, the particle concentration of the light adjustment suspension greatly varies with respect to the target. This causes a problem that a difference in appearance can occur.

This invention is made | formed in view of the above conventional trouble, and makes it a subject to achieve the following objectives.
That is, the object of the present invention is to produce a light control suspension capable of accurately and accurately determining the particle concentration in the light control particle dispersion and suppressing the occurrence of variations in the light control particle concentration in the light control suspension. It is to provide a method. Similarly, another object of the present invention is to provide a method for manufacturing a light control material capable of suppressing the occurrence of variations in the concentration of light adjusting particles .
Furthermore, the objective of this invention is providing the light control film (group) which can suppress generation | occurrence | production of the malfunction which can produce the dispersion | variation in the transmittance | permeability and an external appearance difference, and the quality was constant, and its manufacturing method.

(1) a step of preparing a light control particle dispersion by dispersing light control particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particle dispersion based on the measured density;
Based on the calculated concentration of the light adjustment particle dispersion, the concentration of the light adjustment suspension obtained from the light adjustment dispersion and the polymer dispersant is determined, and a light adjustment suspension having the concentration is prepared. Process,
A method for producing a light-conditioning suspension, comprising:

(2) a step of preparing a light adjusting particle dispersion by dispersing the light adjusting particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particle dispersion based on the measured density;
Based on the calculated concentration of the light adjustment particle dispersion, the concentration of the light adjustment suspension obtained from the light adjustment dispersion and the polymer dispersant is determined, and a light adjustment suspension having the concentration is prepared. Process,
Mixing the prepared light control suspension and a polymer medium that is cured by irradiation with energy rays;
A method for producing a light-modulating material comprising:

(3) a step of preparing a light control particle dispersion by dispersing the light control particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particle dispersion based on the measured density;
Based on the calculated concentration of the light adjustment particle dispersion, the concentration of the light adjustment suspension obtained from the light adjustment dispersion and the polymer dispersant is determined, and a light adjustment suspension having the concentration is prepared. Process,
Mixing the prepared light-adjusting suspension and a polymer medium that is cured by irradiation with energy rays to produce a light-modulating material;
Applying the prepared light-modulating material on a transparent conductive substrate, irradiating energy rays to cure the polymer medium, and forming a light-modulating layer;
The manufacturing method of the light control film characterized by including.

(4) The light control film group manufactured by performing the manufacturing method of the light control film as described in said (3) in multiple times.

According to the present invention may reproduce the particle concentration of the light control particle dispersion, because it is possible to accurately calculate any case, the light control suspension light adjusting particle concentration variation occurred in the light control suspension was suppressed A liquid can be produced. Moreover, the manufacturing method of the light control material which can manufacture the light control material by which generation | occurrence | production of the variation of the light control particle density | concentration was suppressed by using the light control suspension can be provided.
Moreover, the film manufactured using this light-adjusting suspension can suppress the occurrence of defects in which the transmittance varies and the appearance is different, and the light control film (group) having a constant quality and the manufacturing method thereof Can be provided.

In each Example and a comparative example, it is the graph which plotted the density of the prepared light adjustment suspension with respect to the light adjustment particle preparation concentration at the time of light adjustment suspension preparation.

The method for producing a light control suspension of the present invention includes a step of preparing a light control particle dispersion by dispersing light control particles in a dispersion medium, a step of measuring the density of the light control particle dispersion, Based on the measured density, the step of calculating the concentration of the light adjustment particle dispersion, and based on the calculated concentration of the light adjustment particle dispersion, obtained from the light adjustment dispersion and the polymer dispersant. Determining the concentration of the light control suspension, and preparing a light control suspension of the concentration.
Moreover, the manufacturing method of the light control material of this invention irradiates an energy beam with the prepared light control suspension after preparing the light control suspension in the manufacturing method of the light control suspension of the said invention. It is characterized by providing the process of mixing with the polymer medium which hardens | cures by this.
Furthermore, the manufacturing method of the light control film of this invention is the application of the light control material produced on the transparent conductive substrate after producing the light control material in the manufacturing method of the light control material of the said invention, It is characterized by providing a step of forming a light control layer by irradiating and curing the polymer medium.
Below, the manufacturing method of the light control suspension of this invention is demonstrated first.

<Method for producing light-adjusting suspension>
In the method for producing a light control suspension of the present invention, first, a light control particle dispersion is prepared. The light control particle dispersion is prepared by dispersing light control particles in a dispersion medium.
Examples of the light control particles include precursors pyrazine-2,3-dicarboxylic acid dihydrate, pyrazine-2,5-dicarboxylic acid dihydrate, pyridine-2,5-dicarboxylic acid monohydrate. A needle-like small crystal of polyiodide obtained by reacting one substance selected from the group consisting of substances, iodine and iodide with nitrocellulose is preferably used. Examples of iodide include calcium iodide. Examples of the polyiodide thus obtained include, for example, the following general formula CaI ₂ (C ₆ H ₄ N ₂ O ₄ ) · XH ₂ O (X: 1 to 2).
CaI _a (C ₆ H ₄ N ₂ O ₄ ) _b · cH ₂ O (a: 3 to 7, b: 1 to 2, c: 1 to 3)
The thing represented by is mentioned. These polyiodides are preferably acicular crystals.

  Further, as light adjusting particles used in the light adjusting suspension for light control film, US Pat. No. 2,041,138 (EH Land), US Pat. No. 2,306,108 (Land) Et al., U.S. Pat. No. 2,375,963 (Thomas), U.S. Pat. No. 4,270,841 (RL Sax) and British Patent 433,455. Light conditioning particles can also be used. The polyiodide crystals known by these patents are obtained by selecting one of pyrazinecarboxylic acid or pyridinecarboxylic acid and reacting with iodine, chlorine or bromine to produce polyiodide, polychloride or polybromide. And so on. These polyhalides are complex compounds in which a halogen atom reacts with an inorganic substance or an organic substance, and their detailed production methods are disclosed, for example, in US Pat. No. 4,422,963 to Sax.

The particle size used for 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 still more preferably 300 to 500 nm.

Further, the ratio of the major axis to the minor axis of the light control particles, that is, the aspect ratio 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. Here, 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.

  In addition, as a method for evaluating the particle diameter of the light control particles in the present invention, a particle size distribution meter using the principle of a photon correlation method or a dynamic light scattering method can be used. In this method, 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. In particular, when using the Zetasizer Nano series manufactured by Sysmex Corporation and assuming that the equivalent diameter output as Z average is the particle diameter, the particle diameter of the light control particles (hereinafter also referred to as “particle diameter determined by particle size distribution measurement”) ) Is preferably 135 to 220 nm, more preferably 140 to 210 nm, and still more preferably 145 to 205 nm.

  This Z average value is a measured value of a different particle size distribution meter based on, for example, the optical correlation method or the dynamic light scattering method, specifically, the long diameter of the light adjusting particle measured by an electron microscope such as the transmission electron microscope described above. It is known to show a good correlation with the short diameter, and is suitable as an index for evaluating the particle diameter.

  The produced light control particles include unreacted substances and by-products, small and large particles, and small and large aspect ratio particles. Usually, it is preferably used after purification. As this purification method, for example, there is a method of performing centrifugation. Centrifugation conditions depend on the amount to be treated, but 3000 to 20000 G is preferable. The number of treatments is preferably 2 or more. After centrifugation, the supernatant is decanted and discarded, and an organic solvent that can be dispersed without agglomeration of particles is added. At this time, although there is no restriction | limiting in the organic solvent to add, It is preferable that 1 or more types of acetate solvents, such as ethyl acetate, butyl acetate, isopentyl acetate, hexyl acetate, are contained, for example. These media may be used alone or in combination of two or more. Moreover, you may use the solvent which melt | dissolved nitrocellulose only when performing a centrifugation process twice or more. At this time, the concentration of nitrocellulose is 3 to 20%, preferably 5 to 15%. Moreover, after adding a solvent, it is good to process with a homogenizer or an ultrasonic wave so that light control particles can be disperse | distributed in a solvent.

  At this time, the particle concentration of the light adjusting dispersion is determined by the amount of the light adjusting particles that have been centrifuged and settled and the amount of the solvent to be added. It is only necessary to accurately measure the amount of particles. However, if the light control particles are evaporated to dryness and become a solid state, it becomes difficult to redisperse in a dispersion medium such as an organic solvent or a polymer. End up. Further, since the solvent for adjusting the dispersion is added without completely drying the solvent that remains slightly after removing the supernatant by inclining, the amount of particles cannot be measured accurately.

  On the other hand, the dispersion medium used for the preparation of the light control particle dispersion includes isopentyl acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, acetone, ethyl methyl ketone, isobutyl ketone, and the like. Among them, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isopentyl acetate, and hexyl acetate can be preferably used.

  In the above light control particle dispersion liquid, conventionally, a small amount of the light control particle dispersion liquid is sampled, the solid weight remaining after heating and drying is used as the particle amount, and the concentration is calculated. However, as described above, it has been found that this method has a large variation depending on the drying conditions, and the reproducibility is low.

  Thus, as a result of intensive studies, the present inventors have found that a method of measuring the density of the light control particle dispersion and determining the concentration from the density value is good. Therefore, in the method for producing a light control suspension of the present invention, a step of measuring the density of the light control particle dispersion, and a step of calculating the concentration of the light control particle dispersion based on the measured density, Is provided. If there is a difference between the density of the particles and the solvent as the medium, it is considered that there is a correlation between the concentration of the particles and the density of the dispersion. As an apparatus for measuring the density of the solvent and the dispersion liquid, it is possible to obtain the density from the 4th place to the 6th place after the decimal point by using a vibration type digital density meter manufactured by Anton Paar.

  In addition, the expression representing the relationship between the density of the light control dispersion and the particle concentration is Dp, Ds, Dsus for the density of the light control particles, the density of the solvent, and the density of the dispersion, and Cp for the particle concentration in the dispersion. Then, it can be determined if the volume of the light control particle dispersion per unit weight is the sum of the volume of the particles and the solvent. The weights of the light control particles and the solvent contained in the unit weight of the light control particle dispersion are Cp / 100 and (100−Cp) / 100, respectively. Each volume is divided by the density to be Cp / (100 · Dp), (100−Cp) / (100 Ds). Therefore, the equation (1) is obtained.

上記式（１）を展開すると、光調整分散液の粒子濃度を求める式（２）なる。

When the above formula (1) is developed, the formula (2) for obtaining the particle concentration of the light adjusting dispersion liquid is obtained.

このとき、Ｄｓｕｓ、Ｄｓは密度計を用いて測定することが可能であるが、固体の密度であるＤｐは測定することができない。ただし、式（２）を展開した下記式（３）のような光調整粒子密度を求める式において、適当な基準となる光調整粒子分散液の濃度を任意に決めるならば、基準となる光調整粒子密度が求まり、その値を式（２）に代入すると、粒子濃度が求められる。ここで求められる粒子濃度は、基準を決めた時の相対値であり、真の値とは言えないが、相対的な比較は可能であることから、事実上問題はない。また、基準となる光調整粒子分散液の濃度を、ある分散液のＮＶ値（乾燥後の光調整粒子分散液の質量／乾燥前の光調整分散液の質量）を採用すればよい。

At this time, Dsus and Ds can be measured using a density meter, but Dp which is the density of the solid cannot be measured. However, if the concentration of the light adjustment particle dispersion liquid as an appropriate reference is arbitrarily determined in the expression for obtaining the light adjustment particle density, such as the following expression (3) obtained by developing the expression (2), the light adjustment as a reference When the particle density is obtained and the value is substituted into the equation (2), the particle concentration is obtained. The particle concentration obtained here is a relative value when the standard is determined and cannot be said to be a true value. However, since a relative comparison is possible, there is virtually no problem. Further, the NV value of a certain dispersion liquid (mass of light adjustment particle dispersion after drying / mass of light adjustment dispersion before drying) may be adopted as the concentration of the light adjustment particle dispersion serving as a reference.

一方、以上のようにして算出した光調整粒子分散液の濃度に基づいて、前記光調整分散液と、高分子分散剤とから得られる光調整懸濁液の濃度を決定し、該濃度の光調整懸濁液を調製する。具体的には、所定の光調整粒子分散液と高分子分散剤を混合した後、加熱しながら溶剤を減圧留去する方法が好ましい。ロータリーエバポレータにアスピーレータやダイヤフラム式もしくは油回転式ポンプを接続し、減圧すると効率的に溶剤を留去できる。

On the other hand, based on the concentration of the light adjustment particle dispersion calculated as described above, the concentration of the light adjustment suspension obtained from the light adjustment dispersion and the polymer dispersant is determined, and the light having the concentration Prepare a conditioned suspension. Specifically, a method in which a predetermined light adjusting particle dispersion and a polymer dispersant are mixed and then the solvent is distilled off under reduced pressure while heating is preferable. When an aspirator, diaphragm type or oil rotary type pump is connected to the rotary evaporator and the pressure is reduced, the solvent can be distilled off efficiently.

  As the polymer dispersant, a polymer medium that will be described later and a material that phase-separates with a resin matrix that is a cured product thereof are used. Preferably, 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.

  For example, a (meth) acrylic acid ester oligomer having an alkyl group and / or a hydroxyl group is preferred, and a (meth) acrylic acid ester oligomer having an alkyl group and a hydroxyl group is more preferred. When such a copolymer is used, one of the monomer units of alkyl group or hydroxyl group has an affinity for the light control particles, and the remaining monomer units are formed as droplets of the light control suspension in the polymer medium. Since it works to maintain it stably, the light adjusting particles are easily dispersed in the light adjusting suspension, and the light adjusting particles are easily induced in the phase-separated liquid droplet during the phase separation. Examples of the (meth) acrylic acid ester oligomer having an alkyl group and / or a hydroxyl group include butyl methacrylate / 2-hydroxyethyl acrylate copolymer, hexyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacryl Octyl acid / 2-hydroxyethyl methacrylate copolymer, decyl methacrylate / 2-hydroxyethyl methacrylate copolymer, undecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, dodecyl methacrylate / 2-hydroxy methacrylate Ethyl copolymer, tridecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, tetradecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, hexadecyl methacrylate / 2-hydroxyethyl methacrylate copolymer Body, and octadecyl methacrylate / 2-hydroxyethyl methacrylate copolymer and the like.

  When synthesizing such a polymer dispersant (meth) acrylic acid ester oligomer having an alkyl group and / or a hydroxyl group, in order to adjust the molecular weight, mercapto fatty acid ester or mercaptan can be used as a chain transfer agent. . Examples of these include n-octyl mercaptopropionate and 2-ethylhexyl mercaptopropionate, and thiols such as butanethiol, hexanethiol, octanethiol, and dodecanethiol. Moreover, these chain transfer agents may form the partial skeleton of a (meth) acrylic acid ester oligomer.

  These polymer dispersants (meth) acrylic acid ester oligomers can be subjected to liquid separation purification using methanol, ethanol, and propanol after synthesis. Further, it can be used after removing low molecular weight by distillation under high vacuum of 10 Pa or less called molecular distillation.

  These polymer dispersant (meth) acrylic acid ester oligomers preferably have a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) of 500 to 20,000, 1,000. More preferably, it is -10,000.

  The (meth) acrylic acid ester oligomer which is these polymer dispersants is preferably 300 to 5,000 mPa · s, and more preferably 500 to 4000 mPa · s under the condition that the viscosity measured by a viscometer is 25 ° C. More preferably.

  Moreover, the light adjustment suspension prepared as described above can be evaluated for variations in the light adjustment function by measuring the density thereof. That is, the density increases in accordance with the amount of particles when charged, but when the same amount is charged, if the density is a value within a narrow range, a product with small variation and stable quality in production can be obtained. However, the density of the light-adjusted suspension after preparation is large and the product quality is not stable if the range of values is wide. Therefore, if the density of the light adjusting suspension is in a narrow range, it can be evaluated that the quality is stable.

<Manufacturing method of light control material>
The light modulating material manufacturing method of the present invention is prepared by irradiating the prepared light adjusting suspension and energy rays after preparing the light adjusting suspension in the light adjusting suspension manufacturing method of the present invention. It is characterized by providing a step of mixing with a polymer medium to be cured.
Also in the method for producing a light control material of the present invention, variations in the light control particles in the light control material to be manufactured are suppressed, and when used in the preparation of a light control film described later, there are variations in transmittance and appearance differences. It is possible to produce a light control film in which the above is suppressed.

  Examples of the polymer medium that is cured by irradiation with energy rays include a polymer composition that contains a polymer compound that is cured by energy rays such as ultraviolet rays, visible rays, and electron beams, and a photopolymerization initiator. 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.

  As the polymer compound having a substituent having an ethylenically unsaturated bond, a silicone resin, an acrylic resin, a polyester resin, and the like are preferable from the viewpoints of ease of synthesis, light control performance, durability, and the like. These resins are substituted with alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, hexyl group, and cyclohexyl group, and phenyl group. It is preferable to have an aryl group such as a naphthyl group from the viewpoints of light control performance and durability.

  Specific examples of the silicone resin include polymer compounds described in, for example, JP-B-53-36515, JP-B-57-52371, JP-B-58-53656, JP-B-61-17863, and the like. Can be mentioned.

  In addition, the silicone-based resin includes, for example, both-end silanol polydimethylsiloxane, both-end silanol polydiphenylsiloxane-dimethylsiloxane copolymer, both-end silanol siloxane polymers such as both-end silanol polydimethyldiphenylsiloxane, and trialkyl such as trimethylethoxysilane. Dehydrogenation condensation reaction and dealcoholization reaction of silane compounds containing ethylenically unsaturated bonds such as alkoxysilane and (3-acryloxypropyl) methyldimethoxysilane in the presence of 2-ethylhexanetin, which is an organotin catalyst. To be synthesized. The form of the resin is preferably a solventless type. That is, when a solvent is used for resin synthesis, it is preferable to remove the solvent after the synthesis reaction. The amount of the ethylenically unsaturated bond-containing silane compound such as (3-acryloxypropyl) methoxysilane is preferably 2 to 30% by weight, and preferably 5 to 18% by weight of the total amount of the raw material siloxane and silane compound. Is more preferable.

The acrylic resin includes, for example, (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid benzyl, main chain forming monomers such as styrene, (meth) acrylic acid, (meth) acrylic A prepolymer was synthesized by copolymerizing ethylenically unsaturated bond-introducing functional group-containing monomers such as hydroxyethyl acid, isocyanatoethyl (meth) acrylate, and glycidyl (meth) acrylate. By reacting monomers such as glycidyl (meth) acrylate, isocyanatoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid, etc. to the prepolymer to react with the functional group of the polymer Can be obtained.
Moreover, the said polyester resin can be easily manufactured by a well-known method.

  The polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography of the polymer compound having a substituent having an ethylenically unsaturated bond is preferably 20,000 to 100,000, and preferably 30,000 to 80. Is more preferable.

  When using the polymer compound having a substituent having an ethylenically unsaturated bond, a photopolymerization initiator that activates radical polymerization when exposed to energy rays can be used. Specifically, 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, (1-hydroxycyclohexyl) phenyl ketone, and the like can be used.

The amount of these photopolymerization initiators used is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the polymer compound having a substituent having an ethylenically unsaturated bond, More preferred are parts by weight. In addition to the polymer compound having a substituent having an ethylenically unsaturated bond, an organic solvent-soluble resin or thermoplastic resin having no substituent having an ethylenically unsaturated bond, for example, gel permeation Polyacrylic acid, polymethacrylic acid, and the like having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 measured by chromatography can be used in combination.
Moreover, you may add additives, such as coloring inhibitors, such as dibutyltin dilaurate, in a polymer medium as needed. Furthermore, the polymer medium may contain a solvent as necessary.

<Manufacturing method of light control film>
In the method for producing a light control film of the present invention, after preparing a light control material in the method for manufacturing a light control material of the present invention, the prepared light control material is applied on a transparent conductive substrate and irradiated with energy rays. And a step of forming a light control layer by curing the polymer medium.
That is, the light control material of the present invention 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.

Also in the method for producing a light control film of the present invention, a light control film is produced using the light control suspension obtained by the method for manufacturing a light control suspension of the present invention described above. It is possible to produce a light control film in which variation is suppressed and variation in transmittance and appearance difference are suppressed.
In addition, the light control film group of the present invention is manufactured by performing the light control film manufacturing method of the present invention a plurality of times, and as described above, in the manufacture of each light control film, Since the light adjustment particle dispersion and the light adjustment suspension prepared after accurately grasping the concentration of the adjustment particles are used, the concentration of the light adjustment particles is small as a whole. The light control film group with few external appearance differences is obtained.

  In the light control layer of the light control film, a liquid light control suspension is dispersed in the form of fine droplets in a resin matrix made of a solid polymer medium. Such 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. However, since the light adjusting particles have an electric dipole moment, when an electric field is applied to the light control film, the light adjusting particles are arranged in a direction parallel to the electric field, so that light incident on the film is transmitted. As described above, the light adjustment particles respond to the applied electric field, thereby adjusting the light transmission amount. As the light dimming particles, needle-like or rod-like particles are preferable.

  The light control film of the present invention is formed by, for example, applying the light control material of the present invention on a transparent conductive substrate, irradiating energy rays to cure the polymer medium, and forming a light control layer. It can be manufactured by bringing a transparent conductive substrate into close contact therewith.

  Specifically, first, 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 is 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 irradiation with the energy beam, or may be brought into close contact with the light control layer during irradiation with the energy beam. Alternatively, a light control layer may be formed on both 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 μm, and more preferably 20 to 100 μm.

  As a method of obtaining a light control material in which the light control suspension is dispersed in a polymer medium in a droplet state, for example, 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.

  In addition, as a method for applying the light-modulating material on the transparent conductive substrate with a constant thickness, it is possible to use 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. In addition, when apply | coating, you may dilute with a suitable solvent as needed. When a solvent is used, drying is required after coating on the substrate. As the solvent, for example, tetrahydrofuran, toluene, heptane, cyclohexane, ethyl acetate, ethanol, methanol, isoamyl acetate, hexyl acetate and the like can be used.

As 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. Moreover, as a transparent substrate, glass, a polymer film, etc. can be used, for example.

  The above glass means a substrate transparent to visible light, etc., in addition to general glass mainly composed of silicon dioxide, glass of inorganic materials of various compositions, organic materials such as transparent acrylic resin, polycarbonate resin, etc. Resin glass using can also be used.

  Examples of the polymer film 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. However, a polyethylene terephthalate film is preferable because it is excellent in transparency and excellent in moldability, adhesiveness, workability, and the like. Although there is no restriction | limiting in particular in the thickness of a transparent substrate, For example, 1-15 mm is preferable in the case of glass, and 10-200 micrometers is preferable in the case of a polymer film.

  The surface resistance value of the transparent conductive substrate is preferably 3 to 600Ω. Moreover, when producing a light control film by narrowing the interval between transparent conductive substrates, in order to prevent a short-circuit phenomenon that occurs due to the mixing of foreign substances, 200-1,000 mm of the conductive film is formed on the transparent conductive film. You may use the board | substrate with which the transparent insulating layer of thickness is formed. When a reflective light control window such as a rear view mirror for automobiles is produced, a thin film of a conductive metal such as aluminum, gold, or silver that is a reflector may be directly used as an electrode.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
(Preparation of light control particle dispersion)
A 8.5 mass% iodine isopentyl acetate solution from iodine (JIS reagent special grade, Wako Pure Chemical Industries, Ltd.) and isopentyl acetate (reagent special grade, Wako Pure Chemical Industries, Ltd.), and nitrocellulose 1 / 4LIG An isopentyl acetate solution of 20.0% by mass nitrocellulose 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 20.9 mass% calcium iodide solution. A 20 L flask was equipped with a stirrer and a condenser, 6905 g of iodine solution and 8723 g of nitrocellulose solution were added, and the flask was heated at a water bath temperature of 35 to 40 ° C. The water ratio (%) in the nitrocellulose 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 nitrocellulose solution was 53.2 g from the added solution mass. After the temperature of the flask contents reached 35 to 40 ° C., 260 g of dehydrated methanol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and 55.6 g of purified water (manufactured by Wako Pure Chemical Industries, Ltd.) were added. And stirred. 1643 g of calcium iodide solution was added, and then 390 g of pyrazine-2,5-dicarboxylic acid (manufactured by Nikka Techno Service Co., Ltd.) was added. The water bath temperature was set to 42 to 44 ° C., and the mixture was stirred for 4 hours and then allowed to cool.

  The resulting synthesis solution is centrifuged at 9260 G for 5 hours, and the supernatant is removed by inclining. The precipitate remaining at the bottom is added with 5 times the mass of the precipitate, isopentyl acetate, and the precipitate is dispersed by ultrasound. After centrifugation at 710G for 10 minutes, the supernatant was centrifuged at 9260G for 3 hours. The supernatant was removed by inclining, and isopentyl acetate 5 times the mass of the precipitate was added to the precipitate remaining at the bottom, and the precipitate was dispersed with ultrasonic waves to prepare a light control particle dispersion.

(Determination of standard particle density)
The density of this light control dispersion was measured at 25.00 ° C. and found to be 0.92854 g / cm ³ . This dispersed liquid was weighed on a 1 g metal plate, dried at 120 ° C. for 1 hour, then weighed again to determine the NV value, which was 6.98%. Using this NV value as the particle concentration and substituting 2.9722 g / cm ³ obtained by substituting into the equation (3) together with the density value as the reference particle density, this value is used in all cases where the particle concentration is determined from the density below. It was.

(Example 2)
(Synthesis of polymer dispersant)
Toluene (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 131 kg, dodecyl methacrylate 185 kg (Kyoeisha Chemical), 2-hydroxyethyl methacrylate 3.8 kg (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.), n- 14.7 kg of hexyl mercaptan (Tokyo Kasei) was added to the kettle and heated to 60 ° C. with stirring under a nitrogen atmosphere. After 1 hour, 1.47 kg of azoisobutyronitrile (special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 64 kg of toluene, and the whole amount was added dropwise. After heating for 21 hours, the mixture was heated to 115 ° C. and stirred for 2 hours. Then, the pressure was reduced and the solvent was distilled off. This was subjected to molecular distillation at 200 ° C. and 1 Pa to remove low molecular weight components to prepare a polymer dispersant. The density of this polymer dispersant was measured and found to be 0.94331 g / cm ³ .

(Preparation of light control particle dispersion)
Light-adjusting particles were produced in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.67% was used and that 69.4 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 58.4 g. After the third centrifugation, isopentyl acetate three times the mass of the precipitate was added to the precipitate remaining at the bottom, and the precipitate was dispersed with ultrasound to prepare a light control particle dispersion. The density of the prepared light adjusting particle dispersion was 0.92854 g / cm ³ and the particle concentration was 9.2091%.

(Preparation of light control suspension)
Add 38.87g of this light-adjusting particle dispersion and 70.08g of polymer dispersant to a 500mL flask and place it on a rotary evaporator. While heating at 80 ° C, start slowly reducing the pressure with an oil rotary pump. Was distilled off and decompression was continued as it was. After 1 hour from the start of pressure reduction, the degree of vacuum was confirmed to be 1000 Pa or less. Next, isopentyl acetate in the same amount as the content weight was added to the flask, and the second dissolution was performed again by the same procedure to prepare a light control suspension. When the density was measured, it was 0.97210 g / cm ³ . The particle concentration in the prepared light adjusting suspension was 4.86% based on the light adjusting particle dispersion and the particle concentration.

Example 3
(Preparation of light control particle dispersion)
To 90 g of the light control particle dispersion prepared in Example 2, 10 g of isopentyl acetate was added and shaken well. The density of this light control particle dispersion was 0.92190 g / cm ³ and the particle concentration was 8.2588%.

(Preparation of light control suspension)
Using 50.97 g of this light control particle dispersion and 82.41 g of polymer dispersant, a light control suspension was prepared as in Example 2. The feed concentration was 4.86%, and the density was measured to be 0.97182 g / cm ³ .

Example 4
(Preparation of light control particle dispersion)
To 80 g of the light control particle dispersion prepared in Example 2, 20 g of isopentyl acetate was added and shaken well. The density of this light control particle dispersion was 0.91569 g / cm ³ and the particle concentration was 7.3565%.

(Preparation of light control suspension)
Using 56.07 g of this light control particle dispersion and 80.73 g of polymer dispersant, a light control suspension was prepared as in Example 2. The feed concentration was 4.86%, and the density was measured to be 0.97178 g / cm ³ .

(Example 5)
(Preparation of light control particle dispersion)
40 g of isopentyl acetate was added to 60 g of the light control particle dispersion prepared in Example 2 and shaken well. The density of this light control particle dispersion was 0.90328 g / cm ³ and the particle concentration was 5.5169%.

(Preparation of light control suspension)
Using 62.18 g of this light control particle dispersion and 67.16 g of polymer dispersant, a light control suspension was prepared as in Example 2. The feed concentration was 4.86%, and the density was measured to be 0.97162 g / cm ³ .

(Example 6)
(Preparation of light control particle dispersion)
To 50 g of the light control particle dispersion prepared in Example 2, 50 g of isopentyl acetate was added and shaken well. The density of this light control particle dispersion was 0.89724 g / cm ³ and the particle concentration was 4.6032.

(Preparation of light control suspension)
Using 73.46 g of this light control particle dispersion and 66.19 g of polymer dispersant, a light control suspension was prepared as in Example 2. The charged concentration was 4.86%, and the density was measured and found to be 0.97152 g / cm ³ .

(Example 7)
(Preparation of light control particle dispersion)
60 g of isopentyl acetate was added to 40 g of the light control particle dispersion prepared in Example 2 and shaken well. The density of this light control particle dispersion was 0.89139 g / cm ³ and the particle concentration was 3.6925%.

(Preparation of light control suspension)
Using 90.62 g of this light control particle dispersion and 65.50 g of polymer dispersant, a light control suspension was prepared as in Example 2. The feed concentration was 4.86%, and the density was measured, and it was 0.97154 g / cm ³ .

(Example 8)
(Preparation of light control particle dispersion)
Using a nitrocellulose solution having a water ratio of 0.56%, 75.0 g of purified water was used to produce light control particles in the same manner as in Example 1. The amount of water in the nitrocellulose solution was 48.8 g. The density of the prepared light control particle dispersion was 0.90626 g / cm ³ and the particle concentration was 5.9636%.

(Preparation of light control suspension)
Using 82.30 g of this light control particle dispersion and 100.30 g of polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 4.67%, and the density was measured, and it was 0.97081 g / cm ³ .

Example 9
(Preparation of light control particle dispersion)
Using a nitrocellulose solution having a water ratio of 0.62% and using 69.1 g of purified water, light-adjusting particles were produced in the same manner as in Example 1. The amount of water in the nitrocellulose solution was 54.1 g. The density of the prepared light adjusting particle dispersion was 0.90280 g / cm ³ and the particle concentration was 5.4440%.

(Preparation of light control suspension)
Using 93.77 g of this light control particle dispersion and 104.30 g of polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 4.67%, and the density was 0.97073 g / cm ³ when measured.

(Example 10)
(Preparation of light control particle dispersion)
Using a nitrocellulose solution having a water ratio of 0.54% and using 72.9 g of purified water, light-adjusting particles were produced in the same manner as in Example 1. The amount of water in the nitrocellulose solution was 47.1 g. The density of the prepared light control particle dispersion was 0.90100 g / cm ³ and the particle concentration was 5.1727%.

(Preparation of light control suspension)
Using 98.04 g of this light control particle dispersion and 103.54 g of polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 4.67%, and the density was measured, and was 0.97056 g / cm ³ .

(Example 11)
(Preparation of light control particle dispersion)
Light adjustment particles were produced in the same manner as in Example 1 using a nitrocellulose solution having a water ratio of 0.60% and 70.6 g of purified water. The amount of water in the nitrocellulose solution was 52.3 g. The density of the prepared light control particle dispersion was 0.90378 g / cm ³ , and the particle concentration was 5.591%.

(Preparation of light control suspension)
Using 88.88 g of this light control particle dispersion and 101.54 g of polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 4.67%, and the density was measured to be 0.97062 g / cm ³ .

(Example 12)
(Preparation of light control suspension)
A light control suspension was prepared as in Example 2 using 89.68 g of the light control particle dispersion prepared in Example 8 and 100.47 g of the polymer dispersant. The charged concentration was 5.05%, and the density was measured to be 0.97321 g / cm ³ .

(Example 13)
(Preparation of light control suspension)
A light control suspension was prepared as in Example 2, using 101.48 g of the light control particle dispersion prepared in Example 9 and 103.77 g of the polymer dispersant. The feed concentration was 5.05%, and the density was measured, and was 0.973323 g / cm ³ .

(Example 14)
(Preparation of light control suspension)
A light control suspension was prepared as in Example 2 using 103.19 g of the light control particle dispersion prepared in Example 10 and 100.25 g of the polymer dispersant. The charged concentration was 5.06%, and the density was 0.97308 g / cm ³ as measured.

(Example 15)
(Preparation of light control suspension)
Using 95.41 g of the light control particle dispersion prepared in Example 11 and 100.22 g of the polymer dispersant, a light control suspension was prepared as in Example 2. The charged concentration was 5.05%, and the density was measured to be 0.97321 g / cm ³ .

(Example 16)
(Preparation of light control suspension)
A light control suspension was prepared as in Example 2 using 97.80 g of the light control particle dispersion prepared in Example 8 and 101.23 g of the polymer dispersant. The charged concentration was 5.45%, and the density was measured, and was 0.975557 g / cm ³ .

(Example 17)
(Preparation of light control suspension)
Using 110.87 g of the light control particle dispersion prepared in Example 9 and 104.33 g of the polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 5.47%, and the density was measured, and was 0.97576 g / cm ³ .

(Example 18)
(Preparation of light control suspension)
Using 118.48 g of the light control particle dispersion prepared in Example 10 and 106.46 g of the polymer dispersant, a light control suspension was prepared as in Example 2. The preparation concentration was 5.44%, and the density was measured to be 0.975540 g / cm ³ .

(Example 19)
(Preparation of light control suspension)
A light control suspension was prepared as in Example 2 using 103.08 g of the light control particle dispersion prepared in Example 11 and 100.09 g of the polymer dispersant. The feed concentration was 5.45%, and the density was measured, and was 0.97528 g / cm ³ .

(Comparative Example 1)
(Synthesis of polymer dispersant)
A polymer dispersant was synthesized in the same manner as in Example 2. The density of this polymer dispersant was measured and found to be 0.94320 g / cm ³ .

(Preparation of light control particle dispersion)
Light control particles were produced in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.72% was used and that 49.0 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 62.8 g. When the NV value of the prepared light-adjusting particle dispersion was the particle concentration, it was 7.28%.

(Preparation of light control suspension)
1743 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The feed concentration was 5.45%, and the density was measured to be 0.97157 g / cm ³ .

(Comparative Example 2)
(Preparation of light control particle dispersion)
Light adjusting particles were prepared in the same manner as in Example 1, except that a nitrocellulose solution having a water ratio of 0.82% was used, and 40.6 g of purified water added together with dehydrated methanol. The amount of water in the nitrocellulose solution was 71.5 g. When the NV value of the prepared light control particle dispersion was the particle concentration, it was 7.00%.

(Preparation of light control suspension)
1813 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The feed concentration was 5.45%, and the density was measured to be 0.97497 g / cm ³ .

(Comparative Example 3)
(Preparation of light control particle dispersion)
Light control particles were prepared in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.83% was used and that 39.4 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 72.4 g. When the NV value of the prepared light control particle dispersion was the particle concentration, it was 6.12%.

(Preparation of light control suspension)
2074 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The feed concentration was 5.45%, and the density was measured, and was 0.975547 g / cm ³ .

(Comparative Example 4)
(Preparation of light control particle dispersion)
Light-adjusting particles were produced in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.85% was used and that 38.1 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 74.1 g. When the NV value of the prepared light control particle dispersion was the particle concentration, it was 6.08%.

(Preparation of light control suspension)
2088 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The preparation concentration was 5.46%, and the density was measured, and was 0.97646 g / cm ³ .

(Comparative Example 5)
(Preparation of light control particle dispersion)
Light control particles were produced in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.88% was used and that 37.3 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 76.8 g. When the NV value of the prepared light control particle dispersion was the particle concentration, it was 5.30%.

(Preparation of light control suspension)
2395 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The preparation concentration was 5.46%, and the density was measured, and was 0.97657 g / cm ³ .

(Comparative Example 6)
(Preparation of light control particle dispersion)
Light-adjusting particles were produced in the same manner as in Example 1 except that a nitrocellulose solution having a water ratio of 0.85% was used and that 33.0 g of purified water added together with dehydrated methanol was used. The amount of water in the nitrocellulose solution was 74.1 g. When the NV value of the prepared light control particle dispersion was defined as the particle concentration, it was 5.20%.

(Preparation of light control suspension)
2441 g of this light control particle dispersion and 2200 g of polymer dispersant were added to a 5 L flask, and a light control suspension was prepared as in Example 2. The preparation concentration was 5.45%, and the density was measured, and was 0.97833 g / cm ³ .

(Polymer dispersant density)
When the density of the polymer dispersant used in Comparative Examples 1 to 6 was measured, it was 0.94320 g / cm ³ .

  FIG. 1 shows a graph in which the density of the prepared light adjustment suspension is plotted against the concentration of the light adjustment particles prepared at the time of preparation of the light adjustment suspension in each of the above Examples and Comparative Examples.

(Standard deviation calculation)
In Examples 2 to 7, the feed concentration was 4.86%. The standard deviation of the density of these light control suspensions was 0.00022.
In Examples 8 to 11, the feed concentration was 4.67%. The standard deviation of the density of these light control suspensions was 0.00011.
In Examples 12 to 15, the feed concentration was 5.05 to 5.06%. The standard deviation of the density of these light control suspensions was 0.00007.
In Examples 16 to 19, the feed concentration was 5.44 to 5.47%. The standard deviation of the density of these light control suspensions was 0.00021.
In Comparative Examples 1 to 6, the feed concentration was 5.45 to 5.46%. The standard deviation of the density of these light control suspensions was 0.00227. The value is 10 times or more of the example.

  As described above, in the examples, since the light adjustment suspension is prepared using the light adjustment particle dispersion liquid in which the concentration of the light adjustment particles is accurately calculated, variation in the particle concentration in the light adjustment suspension is suppressed. It can also be seen that the density of the light control suspension is within a narrow range. On the other hand, in the comparative example, since the concentration was calculated based on the NV value as in the past, variation in the concentration was recognized.

(Manufacture of polymer media)
In a four-necked flask equipped with a Dean-Stark trap, a condenser, a stirrer, and a heating device, 15.0 g of (3-acryloxypropyl) methyldimethoxysilane (trade name: KBM-5102, manufactured by Shin-Etsu Chemical Co., Ltd.) , 1.9 g of distilled water, 37.5 g of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 8.9 g of a mixed solvent of ethanol / methanol = 9/1 by mass ratio, heated to 65 ° C. and heated for 5 hours Reacted. After the reaction solution was cooled to 40 ° C. or lower, the pressure was reduced to 300 Pa or lower, the temperature was raised to 70 ° C., and a desolubilization step was performed for 2 hours. Then, it cooled to room temperature and obtained 140.0g of compounds which converted a part of alkoxysilane into silanol. The conversion rate to silanol was 54.5%.

The conversion rate of alkoxysilane to silanol is determined based on the intensity (A) of a peak derived from a hydroxyl group (near 3435 cm ⁻¹ ) and the intensity (B) of a peak derived from an alkoxy group (near 2835 cm ⁻¹ ) in infrared spectroscopy. = A / (A + B) × 100. From the infrared spectroscopic measurement after conversion of dimethoxysilane to silanol, (A) was Abs = 0.250, and (B) was Abs = 0.221, so the conversion rate was calculated to be 54.5%.

  In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, both ends silanol polydimethylsiloxane (trade name: X-21-3114, manufactured by Shin-Etsu Chemical Co., Ltd.) 44.0 g, both Terminal silanol polydimethyldiphenylsiloxane (trade name: X-21-3193B, manufactured by Shin-Etsu Chemical Co., Ltd.) 156.0 g, 22.0 g obtained by converting the methoxy group of KBM-5102 to silanol, bis (2-ethyl) Hexanoic acid) tin (trade name: KCS-405T, manufactured by Johoku Chemical Industry Co., Ltd.) (0.01 g) was charged, and the reaction was carried out by refluxing in heptane at 100 ° C. for 5 hours. The temperature was cooled to 50 ° C., 168.0 g of trimethylethoxysilane (trade name: KBM-31, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was refluxed again at 85 ° C. for 2 hours to cause an end cap reaction. Next, the temperature was cooled to 75 ° C. and diethyl phosphate (also known as ethyl acid phosphate) (trade name: JP-502, manufactured by Johoku Chemical Co., Ltd.) 0.01 g (dehydration condensation catalyst bis (2-ethylhexanoic acid)) 100 parts by mass with respect to 100 parts by mass) was added and stirred for 20 minutes, and then cooled to 30 ° C. Next, 210 g of methanol and 90 g of ethanol were added and stirred for 20 minutes. After standing for 12 hours, the alcohol layer was removed, the pressure was reduced to 300 Pa or lower, the temperature was raised to 115 ° C., desolubilization was performed for 5 hours, and 188.3 g of a polysiloxane resin having a weight average molecular weight of 49,000 as a polymer medium. Got. From the hydrogen integration ratio of NMR, the number of repeating units of 3-acryloxypropylmethylsiloxane of this resin was 3.5%.

(Preparation of light control material)
31.3 g of the above polymer medium, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by Ciba Specialty Chemicals) and tetrahydrofuran (Wako Pure Chemicals, special grade) as photopolymerization initiators. Each 0.2 g, 2.5 g of the light control suspension prepared in Example 2 and 5.9 g of isodecyl trimellitic acid (manufactured by Kao) were mixed and stirred to prepare a light control material.

(Preparation of light control film)
Transparent conductivity made of a PET film (300R, manufactured by Toyobo Co., Ltd., thickness 125 μm) having a surface electrical resistance value of 200 to 700 Ω coated with a transparent conductive film (thickness 300 mm) of ITO (indium tin oxide) The light control material was applied on the entire surface of the transparent conductive film of the resin base material. Subsequently, the same transparent conductive resin base material on which a primer layer was similarly formed was laminated and adhered so that the transparent conductive film faced the coating layer of the light control material. Finally, 3000 mJ / cm ² of ultraviolet light is irradiated from the polyester film side of the laminated transparent conductive resin base material using a metal halide lamp, and the light control suspension is turned into a spherical droplet in the UV cured resin matrix. A light-controlling film having a thickness of 330 to 350 μm was produced in which a light-controlling layer having a thickness of 90 to 98 μm formed by dispersion was sandwiched between transparent conductive resin substrates.
→ This paragraph was a long sentence, so it was divided into three parts (no errors were made).

(Measurement of transmittance of light control film)
Using a spectroscopic color difference meter SZ-Σ90 (manufactured by Nippon Denshoku Industries Co., Ltd.), the Y value (%) measured with an A light source and a viewing angle of 2 degrees was defined as light transmittance. The light transmittance was measured when an electric field was applied and when it was not applied. In addition, when an electric field was applied, the transmittance when applying an AC voltage (effective value) of 100 Hz at 50 Hz was Ton (%), and when no voltage was applied, Toff (%), and the value was recorded 60 seconds after the application. Ton was 58.13% and Toff was 0.36%, respectively.

(Example 21)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Example 3 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 58.04% and Toff was 0.44%, respectively.

(Example 22)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Example 4 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 58.24% and Toff was 0.39%, respectively.

(Example 23)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Example 4 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 59.35% and Toff was 0.40%, respectively.

(Example 24)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Example 5 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Each Ton was 60.48% and Toff was 0.44%.

(Example 25)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Example 6 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 59.32% and Toff was 0.46%, respectively.

(Comparative Example 7)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 1 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 62.63% and Toff was 0.96%.

(Comparative Example 8)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 2 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 59.96% and Toff was 0.55%, respectively.

(Comparative Example 9)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 3 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Each Ton was 57.90% and Toff was 0.34%.

(Comparative Example 10)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 4 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Each Ton was 49.60% and Toff was 0.34%.

(Comparative Example 11)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 5 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 52.52% and Toff was 0.24%, respectively.

(Comparative Example 12)
(Preparation of light control material, preparation of light control film, measurement of transmittance)
A light control material was prepared in the same manner as in Example 20 except that the light control suspension prepared in Comparative Example 6 was used, a light control film was prepared using the light control material, and the transmittance was measured. did. Ton was 49.70% and Toff was 0.18%, respectively.

(Standard deviation calculation)
In Examples 20 to 25, the standard deviation of Ton was 0.96, and Toff was 0.04. On the other hand, in Comparative Examples 7 to 12, the standard deviation of Ton was 5.55 and Toff was 0.29. The value is 5 times or more that of the example. From these comparisons, it can be seen that the light control film of the present invention has little variation in transmittance.

Claims (3)

A step of preparing a light control particle dispersion by dispersing the light control particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particles in the light control particle dispersion based on the measured density;
Based on the calculated concentration of the light adjustment particle dispersion, the concentration of the light adjustment particles in the light adjustment suspension obtained from the light adjustment particle dispersion and the polymer dispersant is determined. Preparing a suspension;
A method for producing a light-conditioning suspension, comprising: A step of preparing a light control particle dispersion by dispersing the light control particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particles in the light control particle dispersion based on the measured density;
Calculated based on the concentration of the light control particles dispersion liquid, and the light adjusting particle dispersion, to determine the concentration of the light control particles in the light control suspension obtained from the polymer dispersing agent, suspension light adjustment the concentration Preparing a suspension;
Mixing the prepared light control suspension and a polymer medium that is cured by irradiation with energy rays;
A method for producing a light-modulating material comprising: A step of preparing a light control particle dispersion by dispersing the light control particles in a dispersion medium;
Measuring the density of the light control particle dispersion;
Calculating the concentration of the light control particles in the light control particle dispersion based on the measured density;
Calculated based on the concentration of the light control particles dispersion liquid, and the light adjusting particle dispersion, to determine the concentration of the light control particles in the light control suspension obtained from the polymer dispersing agent, suspension light adjustment the concentration Preparing a suspension;
Mixing the prepared light-adjusting suspension and a polymer medium that is cured by irradiation with energy rays to produce a light-modulating material;
Applying the prepared light-modulating material on a transparent conductive substrate, irradiating energy rays to cure the polymer medium, and forming a light-modulating layer;
The manufacturing method of the light control film characterized by including.

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