JP2012037558A - Light-controlling structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-controlling structure excellent in stability of transmittance for rays with lapse of time.SOLUTION: A light-controlling structure 20 comprises a layer structure including: two transparent conductive resin substrates 25; a light-controlling layer comprising a resin matrix 28 and a light-controlling suspension liquid 27 dispersed in the resin matrix, held between the two transparent conductive resin substrates; two transparent bodies 24 laminated to interpose the transparent conductive resin substrates and the light-controlling layer; and a sealing tape 22 containing butyl rubber and an inorganic material and covering side faces of the laminate including the transparent bodies, the transparent conductive resin substrates and the light-controlling layer.

Description

  The present invention relates to a dimmable structure.

  There is known a light control glass having a structure in which a liquid state light control suspension is injected between two transparent conductive substrates having a narrow interval (see, for example, Patent Document 1). In this light control glass, in a state where no electric field is applied to the liquid light control suspension injected between the two transparent conductive substrates, the light dispersed in the light control suspension 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. Further, when an electric field is applied to the light control glass, an electric field is formed in the light adjustment suspension through the transparent conductive substrate, and the light adjustment particles representing the light adjustment function are polarized and arranged in parallel to the electric field. Light is transmitted between the adjusting particles and the light adjusting particles, and finally the light control glass becomes transparent.

  With respect to the light control glass having such a configuration, a light control film using a film-shaped light control layer instead of a liquid light control suspension has been proposed for the purpose of improving various performances (for example, Patent Documents). 2).

US Pat. No. 1,955,923 JP 2002-189123 A

The light control film as described above is integrated with glass or the like to form a product form. Such a light control film is dark when the power is off and transparent when it is on. Maintaining a dark color for a long time when off is effective for privacy and heat insulation in glass, but these are often used for windows exposed to wind and rain, etc. The long-term stability of performance (particularly maintaining a dark color when off) is not sufficient, and the light transmittance in a state where no electric field is applied may increase with time.
An object of the present invention is to provide a dimming structure having excellent light transmittance over time.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, it has been found that the above-mentioned problems can be solved by sandwiching the light control film with a transparent body and treating the end thereof as follows.
That is, the present invention provides the following inventions.

<1> Two transparent conductive resin base materials, a light control layer that is sandwiched between the two transparent conductive resin base materials, and includes a resin matrix and a light control suspension dispersed in the resin matrix; Two transparent bodies laminated so as to sandwich the transparent conductive resin base material and the light control layer, and a laminate including the transparent body, the transparent conductive resin base material, and the light control layer, including butyl rubber and an inorganic material And a sealing tape that covers a side surface of the body.

<2> The dimmable structure according to <1>, wherein the transparent body is at least one selected from glass, acrylic resin, polycarbonate resin, vinyl chloride resin, polyester resin, and polyolefin resin.

<3> The dimmable structure according to <1> or <2>, wherein the inorganic material is a metal foil containing aluminum.

<4> The sealing tape according to any one of <1> to <3>, wherein the tape includes a polyethylene net as a tape base material.

  ADVANTAGE OF THE INVENTION According to this invention, the light control structure which is excellent in the temporal stability of light transmittance can be provided.

It is a schematic sectional drawing which shows the one aspect | mode of the light control film concerning this invention. 2A is a schematic cross-sectional view for explaining the operation when the electric field of the light control film of FIG. 1 is not applied, and FIG. 2B is a liquid state when the electric field is not applied. It is a figure which shows the mode of the droplet 3 of this light adjustment suspension liquid. 3A is a schematic cross-sectional view for explaining the operation when the electric field of the light control film of FIG. 1 is applied, and FIG. 3B is a liquid state when the electric field is applied. It is a figure which shows the mode of the droplet 3 of this light adjustment suspension liquid. It is a schematic sectional drawing which shows an example of the laminated constitution of the light control structure of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the light control structure of this invention.

In the present specification, a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto, (meth) acrylate means acrylate and corresponding methacrylate, (meth) acryloyl group means acryloyl group and Means the corresponding methacryloyl group.

  The dimming structure of the present invention comprises two transparent conductive resin base materials, a resin matrix sandwiched between the two transparent conductive resin base materials, and a light control suspension dispersed in the resin matrix. Including a light control layer, two transparent bodies laminated so as to sandwich the transparent conductive resin base material and the light control layer, butyl rubber and an inorganic material, the transparent body, the transparent conductive resin base material, And a sealing tape that covers the side surface of the laminate having the light control layer.

With this configuration, the light transmittance of the dimming structure in a state where no electric field is applied is stabilized over a long period of time. This is considered to be because, for example, the moisture resistance of the light controllable structure is improved by sealing the light control film composed of the transparent conductive resin base material and the light control layer with a transparent body and a sealing tape. Can do.
Hereinafter, each layer configuration will be described.

<Light control layer>
The light control layer in this invention consists of a light control material containing the resin matrix and the light control suspension disperse | distributed in this resin matrix. The resin matrix is made of a polymer medium, and the light adjustment suspension is dispersed in a dispersion medium in a state where the light adjustment particles can flow. As the polymer medium and the dispersion medium (dispersion medium in the light control suspension), those in which the polymer medium and its cured product and the dispersion medium can be phase-separated at least when they are formed into a film are used. That is, it is preferable to use a polymer medium and a dispersion medium that are incompatible or partially compatible with each other.

(Polymer medium)
The polymer medium used in the present invention includes (A) a resin having a substituent having an ethylenically unsaturated bond and (B) a photopolymerization initiator, and is irradiated with energy rays such as ultraviolet rays, visible rays, and electron beams. What hardens | cures by doing is mentioned.
(A) As a resin 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 have as substituents alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, hexyl, and cyclohexyl groups, and In view of light control performance and durability, it is preferable to have at least one selected from aryl groups such as phenyl group and naphthyl group.

  Specific examples of the silicone resin include resins described in JP-B-53-36515, JP-B-57-52371, JP-B-58-53656, JP-B-61-17863, and the like. be able to.

  Examples of the silicone-based resin include: Silanol polydimethylsiloxane having both terminals such as silanol polydimethylsiloxane having both terminals, silanol polydiphenylsiloxane-dimethylsiloxane copolymer having both terminals, silanol polydimethyldiphenylsiloxane having both terminals, and trialkylalkoxysilane such as trimethylethoxysilane. A dehydrogenative condensation reaction and a dealcoholization reaction of an ethylenically unsaturated bond-containing silane compound such as (3-acryloxypropyl) methyldimethoxysilane in the presence of an organotin catalyst such as 2-ethylhexanetin; Synthesized. As the silicone resin, a solventless type is preferably used. That is, when a solvent is used for the synthesis of the silicone resin, it is preferable to remove the solvent after the synthesis reaction.

In addition, in the preparation blending of various raw materials at the time of production of the silicone resin, the blending amount of the ethylenically unsaturated bond-containing silane compound such as (3-acryloxypropyl) methoxysilane is 19 to 50 of the total amount of the raw material siloxane and the silane compound. It is preferable to set it as mass%, and it is more preferable to set it as 25-40 mass%.
When the blending amount of the ethylenically unsaturated bond-containing silane compound is 19% by mass or more, it is possible to suppress that the ethylenically unsaturated bond concentration of the finally obtained resin is too lower than the desired concentration. Moreover, it can suppress that the ethylenically unsaturated bond density | concentration of resin obtained becomes higher than a desired density | concentration because it is 50 mass% or less.

  As specific examples of the acrylic resin, 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, A prepolymer is synthesized once by copolymerizing a functional group-containing monomer for introducing an ethylenically unsaturated bond such as hydroxyethyl (meth) acrylate, isocyanate ethyl (meth) acrylate, glycidyl (meth) acrylate, Next, monomers for introducing ethylenically unsaturated bonds such as glycidyl (meth) acrylate, isocyanate ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid, etc. to react with the functional groups of this prepolymer Can be obtained by addition reaction to the prepolymer.

Moreover, there is no restriction | limiting in particular as said polyester resin, It can select suitably from the polyester resin used normally.
As a method for introducing a substituent having an ethylenically unsaturated bond into a polyester resin, an addition reaction of a monomer for introducing an ethylenically unsaturated bond with the polyester resin can be mentioned as in the case of the acrylic resin.

  The weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography of these (A) resins having an ethylenically unsaturated bond is preferably 20,000 to 100,000, and preferably 30,000 to 80,000. More preferably.

The content of the ethylenically unsaturated bond in the resin having an ethylenically unsaturated bond is preferably 0.3 mol / kg to 0.5 mol / kg. When the content is 0.3 mol / kg or more, the end of the light control film can be easily processed, and the opposing transparent electrodes are less likely to be short-circuited, and the electrical reliability tends to be improved. There is. On the other hand, when the concentration is 0.5 mol / kg or less, the polymer medium cured is less likely to dissolve in the dispersion medium constituting the droplets of the light adjustment suspension, and the movement of the light adjustment particles is facilitated. Therefore, the light control performance tends to be improved.
(A) The ethylenically unsaturated bond concentration of the resin having an ethylenically unsaturated bond is determined, for example, from the integral intensity ratio of hydrogen in ¹ H-NMR. Further, when the conversion rate of the charged raw material to the resin is known, it can be obtained by calculation.

  Examples of the (B) photopolymerization initiator used for the polymer medium include J.I. Photochem. Sci. Technol. 2, 283 (1977) and the like can be used without particular limitation. 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) phenylketone, and the like can be used.

  (B) It is preferable that the usage-amount of a photoinitiator is 0.1-20 mass parts with respect to 100 mass parts of said (A) resin, and it is more preferable that it is 0.2-10 mass parts. .

  In addition to the above (A) resin having a substituent having an ethylenically unsaturated bond, an organic solvent-soluble resin or a thermoplastic resin, for example, a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography May be used together as a constituent material of the polymer medium.

  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, and as the solvent, tetrahydrofuran, toluene, heptane, cyclohexane, ethyl acetate, ethanol, methanol, isoamyl acetate, hexyl acetate, or the like can be used.

(Light control suspension)
The light adjusting suspension used in the present invention is one in which light adjusting particles are dispersed in a dispersion medium so as to be flowable. As a dispersion medium in the light control suspension, it plays the role of a dispersion medium in the light control suspension, and selectively adheres and coats the light control particles, and the light control is performed during phase separation from the polymer medium. It is preferable to use a liquid copolymer that acts to move the particles into phase-separated droplet phases, has no electrical conductivity, and has no affinity for the polymer medium.

  As the liquid copolymer, for example, a (meth) acrylic acid ester oligomer having at least one of a fluoro group and a hydroxyl group is preferable, and a (meth) acrylic acid ester oligomer having a fluoro group and a hydroxyl group is more preferable. When such a liquid copolymer is used, one monomer unit of either a fluoro group or a hydroxyl group is directed to the light control particle, and the remaining monomer unit is stabilized as a droplet in the polymer medium in the light control suspension. Since it works to maintain, the light conditioning particles are very homogeneously dispersed in the light conditioning suspension and are efficiently guided into the phase-separated droplets during phase separation.

Examples of the (meth) acrylic acid ester oligomer having at least one of a fluoro group and a hydroxyl group include those copolymerized using at least one of a fluoro group-containing monomer and a hydroxyl group-containing monomer.
Specifically, 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 3,5,5-trimethylhexyl acrylate / 2-hydroxypropyl acrylate / fumar Acid copolymer, butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl acrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, acrylic acid 1H , 1H, 5H-octafluoropentyl / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer Coalescence, 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl crylate copolymer, 2,2,3,3-tetrafluoropropyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 1H, 1H, 5H-octafluoropentyl methacrylate / Examples thereof include butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl / butyl acrylate / acrylic acid 2-hydroxyethyl copolymer.

  These (meth) acrylic acid ester oligomers preferably have a standard polystyrene equivalent weight average molecular weight of 1,000 to 20,000 as measured by gel permeation chromatography (GPC), and 2,000 to 10,000. It is more preferable that

It is preferable that the usage-amount of the fluoro group containing monomer used as the raw material of these (meth) acrylic acid ester oligomers is 6-12 mol% of the monomer total amount which is a raw material, More effectively, it is 7-8 mol%. is there. When the usage-amount of a fluoro group containing monomer is 12 mol% or less, it can suppress that a refractive index becomes large too much and can suppress that a light transmittance falls.
Moreover, it is preferable that the usage-amount of the hydroxyl-containing monomer used as the raw material of these (meth) acrylic acid ester oligomers is 0.5-22.0 mol%, and is 1-8 mol% more effectively. When the usage-amount of a hydroxyl-containing monomer is 22.0 mol% or less, it can suppress that a refractive index becomes large too much and can suppress that a light transmittance falls.

As the light adjusting particles, for example, a polymer medium or a resin component in the polymer medium, that is, a resin having a low affinity with (A) a resin having a substituent having an ethylenically unsaturated bond is preferable. Further, in the presence of a polymer dispersant capable of enhancing the dispersibility of the light control particles, pyrazine-2,3-dicarboxylic acid dihydrate, pyrazine-2,5-dicarboxylic, which is a precursor of the light control particles, is used. Polyiodide needles made by reacting one substance selected from the group consisting of acid dihydrate and pyridine-2,5-dicarboxylic acid monohydrate with iodine and iodide Small crystals are preferably used.
Examples of the polymer dispersant that can be used include nitrocellulose. Examples of iodide include calcium iodide.

The polyiodide obtained in this way, for example, the following formula _{CaI 2 (C 6 H 4 N} 2 O 4) · xH 2 O (x: 1~2)
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 either of these 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 crystals of polyiodide known by these patents can be obtained by selecting one of pyrazinecarboxylic acid and pyridinecarboxylic acid and reacting with iodine, chlorine or bromine, etc. It is produced by making it a polyhalide. 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.

As disclosed by Sachs, in the process of synthesizing the light control particles, to form light control particles of a uniform size and to improve the dispersibility of the light control particles in a specific dispersion medium As described above, it is preferable to use a polymer material such as nitrocellulose as the polymer dispersant. However, when nitrocellulose is used, crystals coated with nitrocellulose are obtained, and when such crystals are used as light control particles, the light control particles do not float in the droplets separated during phase separation, May remain in the resin matrix.
In order to prevent this, it is preferable to use a silicone resin having a substituent having an ethylenically unsaturated bond as the resin (A) having a substituent having an ethylenically unsaturated bond in the polymer medium. When a silicone resin is used as the polymer medium, the light control particles easily disperse and float in the fine droplets formed by phase separation during film production, resulting in better variable capacity. Can be obtained.

  In addition to the above-mentioned light control particles, for example, inorganic fibers such as carbon fibers, phthalocyanine compounds such as τ-type metal-free phthalocyanine, metal phthalocyanine, and the like can be used. In the phthalocyanine compound, examples of the central metal include copper, nickel, iron, cobalt, chromium, titanium, beryllium, molybdenum, tungsten, aluminum, and chromium.

  In the present invention, the size of the light adjusting particles is preferably 1 μm or less, more preferably 0.1 to 1 μm, and further preferably 0.1 to 0.5 μm. When the size of the light adjusting particles exceeds 1 μm, light scattering occurs, or the orientation movement in the light adjusting suspension decreases when an electric field is applied. May occur. The size of the light control particles is a value of a volume average particle diameter measured by a photon correlation spectroscopy measured with a submicron particle analyzer (for example, product name: N4MD (manufactured by Beckman Coulter)).

  The light control suspension used in the present invention preferably comprises 1 to 70% by weight of light control particles and 30 to 99% by weight of dispersion medium, and 4 to 50% by weight of light control particles and 50 to 96% of dispersion medium. % Is more preferable. In the present invention, the refractive index of the polymer medium and the refractive index of the dispersion medium are preferably approximated. Specifically, the difference in refractive index between the polymer medium and the dispersion medium in the present invention is preferably 0.005 or less, more preferably 0.003 or less. The light-modulating material usually contains 1 to 100 parts by mass, preferably 6 to 70 parts by mass, and more preferably 6 to 60 parts by mass of the light adjustment suspension with respect to 100 parts by mass of the polymer medium.

<Primer layer>
In order to improve the adhesion between the two transparent conductive resin base materials and the light control layer sandwiched between them, a primer layer may be provided between the transparent conductive resin base material and the light control layer as necessary. preferable.
The primer layer can be formed, for example, by curing at least one of urethane (meth) acrylates with a thermal polymerization initiator or a photopolymerization initiator, and includes oxide fine particles (fillers) as necessary. Also good.

  As a primer layer material in the present invention, for example, urethane (meth) acrylate containing a pentaerythritol skeleton will be described. Examples of urethane (meth) acrylates containing a pentaerythritol skeleton include compounds represented by any one of (Formula 1) to (Formula 7).

  Note that R in (Formula 5) to (Formula 7) is a hydrogen atom or (meth) acryloyl group shown below, and each R may be the same or different, and at least one of them is hydrogen. An atom is preferred.

  Among the above, it is preferable to use at least one urethane (meth) acrylate having an isophorone diisocyanate skeleton for the primer layer.

The urethane (meth) acrylate containing the pentaerythritol skeleton used in the present invention can be obtained by the following method.
Urethane (meth) acrylates containing a pentaerythritol skeleton can be synthesized by known methods. For example, since urethane (meth) acrylate is generally obtained by reacting an isocyanate group of a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate by a known method, the same applies to urethane acrylate containing a pentaerythritol skeleton. In addition, for example, it can be produced by any one of the following production methods 1 to 4.

(Production method 1): A method in which a polyol compound, a polyisocyanate compound, and a pentaerythritol skeleton-containing (meth) acrylate are charged together and reacted.
(Production method 2): A method in which a polyol compound and a polyisocyanate compound are reacted, and then a pentaerythritol skeleton-containing (meth) acrylate is reacted.
(Production Method 3): A method in which a polyisocyanate compound and a pentaerythritol skeleton-containing (meth) acrylate are reacted, and then a polyol compound is reacted.
(Production Method 4): A method in which a polyisocyanate compound and a pentaerythritol skeleton-containing (meth) acrylate are reacted, then a polyol compound is reacted, and finally a pentaerythritol skeleton-containing (meth) acrylate is reacted.
Moreover, a catalyst may be used for these manufacturing methods, for example, a tin-based catalyst such as dibutyltin laurate, a tertiary amine-based catalyst, or the like is used.

  Examples of the pentaerythritol skeleton-containing (meth) acrylate used in the above production methods 1 to 4 include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol. Examples thereof include a hydroxyl group-containing (meth) acrylate such as tetra (meth) acrylate.

  Examples of the polyisocyanate compound used in the above production methods 1 to 4 include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-diphenylmethane diisocyanate, 4,4 ′ -Biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), methylene bis (4- Cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4,4′-diphenyl Examples thereof include propane diisocyanate and lysine diisocyanate.

  As urethane (meth) acrylate containing pentaerythritol skeleton, commercially available products containing urethane (meth) acrylate containing pentaerythritol skeleton can also be used. For example, UA-306H, UA-306I, UA-306T, UA -510H (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

  Urethane (meth) acrylates containing both a pentaerythritol skeleton and an isophorone diisocyanate skeleton (hereinafter sometimes abbreviated as “IPDI skeleton”) use isophorone diisocyanate as the polyisocyanate compound among the above production methods 1 to 4. Can be obtained.

Moreover, a commercial item can also be used and can illustrate specifically as a commercial item containing the urethane acrylate containing both a pentaerythritol skeleton and an IPDI skeleton.
AY42-151 (containing SiO ₂ fine particles as filler, manufactured by Toray Dow Corning Co., Ltd.), UVHC3000 (containing no filler, manufactured by Momentive Performance Materials LLC), UVHC7000 (containing no filler, Momentive Performance Materials) And the like).

  As a material for forming the primer layer, in addition to the urethane (meth) acrylate containing the IPDI skeleton, a (meth) acrylate having a hydroxyl group may be mixed and used in combination. More preferably, (meth) acrylate having a pentaerythritol skeleton is used in combination as (meth) acrylate having a hydroxyl group. Specific examples of the (meth) acrylate having a hydroxyl group include compounds represented by any one of the following (formula 8) to (formula 15).

  The (meth) acrylate having a hydroxyl group in the molecule can be synthesized by a known method. For example, in the case of an epoxy ester such as (Formula 8) and (Formula 9), an epoxy compound and (meth) acrylic acid are reacted in the presence of an esterification catalyst and a polymerization inhibitor in an inert gas. Can be obtained.

Examples of the inert gas include nitrogen, helium, argon, carbon dioxide and the like. These can be used alone or in combination.
As the esterification catalyst, compounds containing tertiary nitrogen such as triethylamine, pyridine derivatives and imidazole derivatives, phosphorus compounds such as trimethylphosphine and triphenylphosphine, or amine salts such as tetramethylammonium chloride and triethylamine salt are used. . The addition amount is usually 0.000001 to 20% by mass, preferably 0.001 to 1% by mass with respect to the epoxy compound.
As the polymerization inhibitor, known polymerization inhibitors such as hydroquinone and tertiary butyl hydroquinone are used. The amount used is usually selected from the range of 0.000001 to 0.1% by mass.

  Examples of the epoxy ester include 2-hydroxy-3-phenoxypropyl acrylate (trade name: Aronix M-5700, manufactured by Toagosei Co., Ltd., or trade name: epoxy ester M-600A, manufactured by Kyoeisha Chemical Co., Ltd.), 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: Light Ester G-201P, manufactured by Kyoeisha Chemical Co., Ltd.), glycerin diglycidyl ether acrylic acid adduct (trade name: epoxy ester 80MFA, Kyoeisha Chemical Co., Ltd.) Manufactured) and the like.

  In the case of a (meth) acrylate having a hydroxyl group and a pentaerythritol skeleton as in (Formula 10) to (Formula 15), pentaerythritol, dipentaerythritol, etc., and acrylic acid or methacrylic acid are used as an esterification catalyst in the air. It can be obtained by reacting in the presence of a polymerization inhibitor. As a reaction method for condensing acrylic acid or methacrylic acid to pentaerythritol or dipentaerythritol, known methods described in JP-B-5-86972, JP-A-63-68642 and the like can be applied.

  Urethane (meth) acrylate containing pentaerythritol skeleton used for primer layer formation, more preferably urethane (meth) acrylate further containing IPDI skeleton, if necessary together with (meth) acrylate having hydroxyl group, start thermal polymerization It is preferable to use as a thin film by curing with an agent or a photopolymerization initiator. There is no restriction | limiting in particular in the thermosetting method and the photocuring method, Each normal hardening method can be applied.

  The thermal polymerization initiator used in the present invention may be any thermal initiator that can be decomposed by heat to generate radicals and initiate polymerization of the polymerizable compound, and useful radical initiators are known initiators, An organic peroxide, an azonitrile, etc. can be mentioned, However, It is not limited to these.

Organic peroxides include alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates, and the like.
Examples of the azonitrile include azobisisobutyronitrile and azobisisopropylnitrile.

  Any photopolymerization initiator may be used as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization of the polymerizable compound. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2, 2 -Dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, Benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2- Tyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like, but are not limited thereto.

The primer layer preferably further contains at least one oxide fine particle.
Examples of oxides that may be contained in the primer layer include SiO ₂ , ITO, ZrO ₂ , TiO ₂ , Bi ₂ O ₃ , Al ₂ O ₃ , Y ₂ O ₃ , CeO ₂ , ZnO, CuO, SnO _2. And cobalt blue. More preferably, it is at least one selected from SiO ₂ , ITO, and ZrO ₂ .

Addition of oxide fine particles as a filler to the primer layer makes it possible to obtain a primer layer with high hardness, which has the effect of making the underlying transparent conductive film less likely to be damaged when the light control film is peeled off and the driving electrode is taken out. is there.
In addition, by adding oxide fine particles to the primer layer, it may be possible to adjust the surface energy of the primer layer to further improve the adhesion.

A preferable particle diameter of the oxide fine particles is 50 nm or less from the viewpoint of suppressing haze increase of the light control film.
In the present invention, the average particle diameter is an average particle diameter calculated using the following formula from a specific surface area measured by a specific surface area measuring apparatus by the BET method.
Average particle diameter (nm) = 6,000 / (density [g / cm ³ ] × specific surface area [m ² / g])

The oxide fine particles having an average particle size in the above range may be appropriately selected from commercially available products.
In addition, the preferable content in the primer layer of oxide microparticles is 30 mass% or less with respect to the whole material of a primer layer from the point of haze raise suppression of a light control film.

  In the present invention, the thickness of the primer layer is preferably 500 nm or less, and more preferably 1 nm to 500 nm. More preferably, it is 10 nm-500 nm, More preferably, it is 10 nm-500 nm, Most preferably, it is 10 nm-100 nm.

When the film thickness is 1 nm or more, sufficient adhesive strength tends to be obtained, and when the film thickness is 500 nm or less, the tackiness of the primer layer is prevented from becoming too strong, and the primer layer is applied and rolled. It is possible to suppress the occurrence of inconvenience that the primer layer is transferred to the back surface of the base film after being wound on, or the base film on the side to be laminated at the time of manufacturing the light control film is difficult to align.
The thickness of the primer layer can be measured by ultraviolet / visible light reflectance spectroscopy, X-ray reflectance measurement, ellipsometry, or the like.

  The primer layer can be provided, for example, by forming a primer layer on a transparent conductive resin substrate. Examples of a method for forming a primer layer on a transparent conductive resin substrate include, for example, a material for forming a primer layer, a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, and a die coater method. , Applied to transparent conductive resin base material using a comma coater method, gravure coating method, micro gravure coating method, roll brush method, spray coating method, air knife coating method, impregnation method, curtain coating method, etc. alone or in combination This can be done.

  In addition, when apply | coating, the material which forms a primer layer may be diluted with a suitable solvent as needed, and the solution of the material which forms a primer layer may be prepared and used. When a solvent is used, drying is required after coating on the transparent conductive resin substrate. In addition, the coating film used as a primer layer may be formed only on one side of a transparent conductive resin base material as needed, and may be formed on both surfaces.

  The solvent used for forming the primer layer may be any solvent that can dissolve the material forming the primer layer and can be removed by drying or the like after forming the coating layer. For example, isopropyl alcohol, ethanol, methanol, 1-methoxy-2-propanol, 2-methoxyethanol, cyclohexanone, methyl isobutyl ketone, anisole, methyl ethyl ketone, acetone, tetrahydrofuran, toluene, heptane, cyclohexane, ethyl acetate, propylene glycol monomethyl ether acetate , Diethyl diglycol, dimethyl diglycol, isoamyl acetate, hexyl acetate and the like, and a mixed solvent thereof may be used.

<Transparent conductive resin substrate>
In the case of producing a light control film using the light control material in the present invention, the transparent conductive resin base material used as a drive electrode generally has a light transmittance of 80 on the transparent resin base material. A transparent conductive resin substrate having a surface resistance value of 3 to 3,000Ω coated with at least% transparent conductive film (ITO, SnO ₂ , In ₂ O ₃ ) can be used.
The light transmittance can be measured according to the total light transmittance measuring method of JIS K7105. Moreover, as a transparent resin base material, a polymer film etc. can be used, for example.

  Examples of the polymer film include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride, acrylic resin films, polyethersulfone films, polyarylate films, polycarbonate films, and the like. Can be mentioned. Among these, 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 conductive film coated on the transparent resin substrate is preferably 10 nm to 5,000 nm.
The thickness of the transparent resin substrate is not particularly limited, but for example, in the case of a polymer film, 10 μm to 200 μm is preferable. A transparent resin in which a transparent insulating layer having a thickness of several nanometers to 1 μm is further formed on a transparent conductive film in order to prevent a short circuit caused by a mixture of different substances, etc. A conductive substrate may be used.

  When the light control film according to the present invention is used for a reflective light control window (for example, a rear view mirror for an automobile), a thin film made of a conductive metal such as aluminum, gold, or silver as a reflector is driven. It may be used directly as a working electrode.

<Light control film>
The light control film of the present invention can be formed using a light control material, and the light control material includes a resin matrix formed from a polymer medium, and a light control suspension dispersed in the resin matrix. And forming a light control layer. The light control layer is sandwiched between two transparent conductive resin base materials having a primer layer for improving adhesion to the light control layer, or a transparent conductive resin base material and a primer layer having a primer layer It is sandwiched between two transparent conductive resin base materials that are transparent conductive resin base materials that do not have any.

In order to obtain a light control film, first, a liquid light adjusting suspension is homogeneously mixed with a polymer medium, and the light adjusting suspension is composed of a mixed liquid dispersed in the polymer medium in the form of droplets. Get a dimming material.
Specifically, it is as follows. A liquid in which the light adjusting particles are dispersed in a solvent and a dispersion medium of the light adjusting suspension are mixed, and the solvent is distilled off with a rotary evaporator or the like to prepare a light adjusting suspension.
Next, 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.

  After applying this light-modulating material to a transparent conductive resin substrate having a primer layer with a certain thickness, the polymer medium is cured by irradiating ultraviolet rays using a high-pressure mercury lamp or the like. As a result, a light control layer in which the light control suspension is dispersed in the form of droplets is formed in the resin matrix made of the cured polymer medium. The light transmittance of the light control layer 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 sticking the transparent conductive resin base material which has another primer layer on the light control layer formed in this way.

Alternatively, after applying this light-modulating material to a transparent conductive resin substrate having a primer layer at a certain thickness, and then laminating it on the transparent conductive resin substrate having the other primer layer, the ultraviolet light is irradiated. The polymer medium may be cured. Only one transparent conductive resin substrate may be sufficient as the transparent conductive resin substrate which has a primer layer.
Furthermore, a light control layer may be formed on each of the two transparent conductive resin substrates, and these 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 μm to 1,000 μm, and more preferably 20 μm to 100 μm.
The droplet size (average droplet diameter) of the light control suspension dispersed in the resin matrix is usually 0.5 μm to 100 μm, preferably 0.5 μm to 20 μm, more preferably 1 μm to 5 μm. . 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. Etc.
The average droplet diameter is calculated, for example, by taking an image such as a photograph from one surface direction of the light control film using SEM, measuring a plurality of arbitrarily selected droplet diameters, and calculating the average value thereof. Can do. It is also possible to capture 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.

  For the application of the light-modulating material to be the light-modulating layer, for example, known coating means such as a bar coater, applicator, doctor blade, roll coater, die coater, and comma coater can be used. When the light-modulating material is applied to the surface of the primer layer provided on the transparent conductive resin substrate, or when using a transparent conductive resin substrate without a primer layer on one side, the transparent conductive resin substrate It can also be applied directly. In addition, when apply | coating, you may dilute a light control material with a suitable solvent as needed. When a solvent is used, it is preferable to dry after coating on the transparent conductive resin substrate.

  Tetrahydrofuran, toluene, heptane, cyclohexane, ethyl acetate, ethanol, methanol, isoamyl acetate, hexyl acetate, etc. can be used as a solvent used for application of the light modulating material.

  In addition, in order to form a light control layer in which a liquid light control suspension is dispersed in the form of fine droplets in a solid resin matrix, the light control material is mixed with a homogenizer, an ultrasonic homogenizer, or the like. It is possible to use a method of finely dispersing the light control suspension in the polymer medium, a phase separation method by polymerization of resin components in the polymer medium, a phase separation method by solvent volatilization, or a phase separation method by temperature. it can.

  According to said method, the light control film which can adjust light transmittance arbitrarily by formation of an electric field is provided. Even when no electric field is formed, the light control film maintains a clear coloring state without light scattering, and is converted into a transparent state when the electric field is formed. This ability exhibits a reversible repeat characteristic of over 200,000 times. In order to enhance the light transmittance in the transparent state and the sharpness in the colored state, it is preferable to match the refractive index of the liquid light adjusting suspension with the refractive index of the resin matrix.

The power source used for operating the light control film is alternating current, and can be in the frequency range of 10 to 100 volts (effective value) and 30 Hz to 500 kHz.
The light control film of this invention can make the response time with respect to an electric field within 1-50 seconds at the time of decoloring, and within 1-100 seconds at the time of coloring.

  In addition, as a result of an ultraviolet irradiation test using 750 W ultraviolet rays or the like, the ultraviolet durability shows a stable variable characteristic even after 250 hours have passed, and even when left at -50 ° C. to 90 ° C. for a long time, It is possible to maintain variable characteristics.

  In the production of a light control film using liquid crystal, which is a conventional technique, when a method using an emulsion using water is used, the liquid crystal often reacts with moisture and loses its light adjustment characteristics. There is a problem that it is difficult. In the present invention, not a liquid crystal, but a liquid light adjusting suspension in which light adjusting particles are dispersed in the light adjusting suspension is used. Therefore, unlike a light control film using liquid crystal, an electric field is applied. Even if not, light is not scattered, and it represents a colored state having excellent definition and no viewing angle limitation. Then, the light variability can be arbitrarily adjusted by adjusting the content of the light adjusting particles, the droplet form and the film thickness, or adjusting the electric field strength. In addition, since the light control film of the present invention does not use liquid crystals, the color change due to ultraviolet exposure and the variable capacity decrease, and the voltage drop generated between the peripheral part and the central part of the transparent conductive resin base material peculiar to large products. The accompanying response time difference is also eliminated.

When an electric field is not applied to the light control film according to the present invention, the light control particles in the light control suspension exhibit a brown color motion, and the light control particles absorb light and show a clear coloring state due to a dichroic effect. However, when an electric field is applied, the light adjusting particles in the droplet or the droplet connected body are arranged in parallel to the electric field and converted into a transparent state.
Although the light control layer is in a film state, there is a problem with the light control glass according to the prior art that uses the liquid light control suspension as it is, that is, the liquid between the two transparent conductive resin substrates. Difficulty in injecting suspension, expansion phenomenon in the lower part due to the water pressure difference between the upper and lower parts of the product, local hue change due to changes in the base interval due to external environment such as wind pressure, sealing between transparent conductive resin base materials The leakage of the light control material due to the destruction of the material is solved.

  Further, in the case of a light control window according to the prior art using liquid crystal, the liquid crystal is easily deteriorated by ultraviolet rays, and the operating temperature range is narrow due to the thermal characteristics of nematic liquid crystal. Furthermore, also in terms of optical characteristics, when no electric field is applied, it shows a milky white translucent state due to light scattering, and even when an electric field is applied, it is not completely sharpened and the milky state is There are remaining problems. Therefore, in such a light control window, a display function based on light blocking and transmission, which is used as an operation principle in existing liquid crystal display elements, is impossible. However, such a problem can be solved by using the light control film according to the present invention.

  The light control film in the present invention has a strong adhesion between the light control layer and the transparent conductive resin base material, and the light control layer is peeled off from the transparent conductive resin base material in a manufacturing process or a processing process after film manufacture. It is an excellent light control film that does not cause any problem.

The structure and operation of the light control film in the present invention will be described in more detail with reference to the drawings.
FIG. 1 is a structural schematic diagram showing one embodiment of a light control film in the present invention. The light control layer 1 is sandwiched between the transparent conductive resin substrates 4 made of the two transparent resin substrates 5b coated with the transparent conductive film 5a. A primer layer 6 is provided between the light control layer 1 and the transparent conductive resin substrate 4. By switching the switch 8, the power supply 7 and the two transparent conductive films 5a are connected or disconnected. The light control layer 1 includes a film-like resin matrix 2 obtained by UV-curing a resin having a substituent having an ethylenically unsaturated bond as a polymer medium, and droplets 3 in the resin matrix 2. It consists of a liquid light control suspension dispersed in

FIG. 2 is a view for explaining the operation of the light control film shown in FIG. 1, and shows a case where the power source 7 is disconnected by the switch 8 and no electric field is applied. In this case, incident light 11 is absorbed by the light adjusting particles 10 due to Brownian motion of the light adjusting particles 10 dispersed in the dispersion medium 9 constituting the droplets 3 of the liquid light adjusting suspension. Scattered or reflected, transmission is suppressed.
On the other hand, as shown in FIG. 3, when an electric field is applied by connecting a power source 7 with a switch 8, the light adjusting particles 10 are arranged substantially parallel to the electric field formed by the applied electric field. It passes between the arranged light adjusting particles 10. In this way, a light transmission function without scattering and a decrease in transparency is provided.

  The light control film in 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.

  As an application method, the light control film is sandwiched between two transparent bodies, and a sealing tape containing butyl rubber and an inorganic material is arranged on the side surface of the laminate composed of the light control film and the two transparent bodies, and the light control film is adjusted. The optical film is used as a sealed state.

<Transparent body>
The transparent body used in the present invention is not particularly limited as long as it has a visible light transmittance of 50% or more, and an inorganic material or an organic material can be used.

  Inorganic materials include soda-lime glass, lead glass, borosilicate glass, soda lime glass, etc. for general construction, glass of various compositions in other applications, heat reflective glass, heat absorbing glass, tempered glass, double tempered glass, semi Functional glass such as tempered glass can also be used.

  Organic materials include polyacrylic resin, polycarbonate resin, polyvinyl chloride resin, polyester resin such as PET and PEN, polystyrene resin, polycycloolefin resin, polyimide resin, polyfluorine resin, polyolefin such as polyethylene and polypropylene, which are transparent resins Resins, epoxy resins, unsaturated polyester resins, polyurethane resins, and the like can be used.

  The shape of these transparent bodies is provided as a sheet from a film, and the thickness can be 50 μm to 20 mm. If the thickness is thin, it is flexible and easy to handle, but the water vapor permeability is increased and the moisture resistance is poor. On the other hand, if the thickness is thick, the water vapor permeability is increased and the moisture-proof property is increased. However, problems such as an increase in product weight and a decrease in transmittance occur.

  These transparent bodies sandwich the light control film from both sides to form a laminate, but may be bonded to the light control film as necessary. Adhesion methods include interlayer film for laminated glass, polyvinyl butyral, ethylene vinyl acetate copolymer, polyurethane sheet, adhesion by curing liquid thermosetting resin such as polyurethane resin, acrylic resin, epoxy resin, silicone resin. There is a method of pressure bonding via an acrylic resin, a silicone resin, a polyester resin or the like as a method and an adhesive material.

<Tape made of butyl rubber and inorganic material>
In the light controllable laminate of the present invention, a sealing tape containing butyl rubber and an inorganic substance is disposed on the side surface of the laminate having the light control film and two transparent bodies sandwiching the light control film, and the light control is performed by the sealing tape. The film is sealed.
The sealing tape containing butyl rubber and an inorganic substance contains butyl rubber and an inorganic substance, and combines the high adhesion of butyl rubber and the low moisture permeability of the inorganic substance.

Although it will not restrict | limit especially if the said sealing tape contains butyl rubber and an inorganic substance, It is preferable to be comprised from the adhesive material containing a butyl rubber, and the base material containing an inorganic substance.
The pressure-sensitive adhesive material is a butyl rubber excellent in adhesion and water resistance, and contains a known non-vulcanized or vulcanized butyl rubber as a component, and other additives as required.

Examples of the base material include paper, a film comprising plastic, a nonwoven fabric, or a net. From the viewpoint of long-term stability of light transmittance, the base material is preferably a nonwoven fabric or a net. More preferably.
Furthermore, the base material further includes an inorganic material such as a metal foil. Examples of the inorganic material include aluminum foil, silver foil, tin foil, lead foil, platinum foil, titanium foil, and vapor deposited films thereof, and vapor deposited films of silica, and are metal foils from the viewpoint of moisture resistance, corrosion resistance, price, and the like. It is preferable that the metal foil contains aluminum (for example, aluminum foil).

From the viewpoint of long-term stability of light transmittance, the base material preferably includes a nonwoven fabric or a net and a metal foil, and more preferably a metal foil including a polyethylene net and aluminum.
Examples of the sealing tape containing butyl rubber and an inorganic material include Sliontec Superbutyl Tape 9290, 9830, and the like.

As a method of disposing a sealing tape on the side surface of a laminate including a light control film and a transparent body, a region including at least a part of the side surface of the transparent body and all of the side surfaces of the light control film on the side surface of the laminate. It suffices if it is covered with the sealing tape.
Moreover, it is preferable that the whole side surface of the said laminated body is coat | covered with the sealing tape from a viewpoint of long-term stability of light transmittance. Further, in addition to the entire side surface of the laminate, it is also possible that at least a part of the surface opposite to the surface facing the light control film of the transparent body constituting the laminate is covered with the sealing tape. preferable.

The method for disposing the sealing tape on the side surface of the laminate including the light control film and the transparent body will be described in more detail with reference to the drawings.
FIG. 4 shows a resin matrix 28, a light control layer containing a liquid light control suspension dispersed in the form of droplets 27 in the resin matrix 28, and a transparent conductive film disposed so as to sandwich the light control layer. Of the light-sensitive resin base material 25, a light control film comprising a primer layer 26 provided between the transparent conductive resin base material 25 and the light control layer 1, and a laminate comprising two transparent bodies 24 sandwiching the light control film It is a schematic sectional drawing which shows an example of the layer structure of the light control structure 20 which has arrange | positioned the sealing tape 22 to the whole side surface, and coat | covered the side surface of a laminated body. A power source is connected to the transparent conductive resin substrate 25 via a switch (not shown).
Further, FIG. 5 shows the side opposite to the surface facing the light control film of the transparent body constituting the laminated body in addition to the entire side surface of the laminated body composed of the light control film and the two transparent bodies 24 sandwiching the light control film. It is a schematic sectional drawing which shows an example of the laminated constitution of the light control structure 30 which has arrange | positioned the sealing tape 22 also to at least one part of this surface, and coat | covered the side surface of a laminated body, and a part of surface and back surface. A power source is connected to the transparent conductive resin substrate 25 via a switch (not shown).
Furthermore, you may provide a space | gap between a light control film and a sealing tape using the transparent body larger than a light control film.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

(Production example of light control particles)
In a 500 ml four-necked flask equipped with a stirrer and a condenser, nitrocellulose 1/4 LIG (trade name, manufactured by Bergerac NC) 15 mass% isoamyl acetate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) Diluted solution 87.54 g, isoamyl acetate 44.96 g, dehydrated CaI ₂ (chemical use, manufactured by Wako Pure Chemical Industries, Ltd.) 4.5 g, absolute ethanol (for organic synthesis, manufactured by Wako Pure Chemical Industries, Ltd.) 2. In a solution of 0 g and purified water (purified water, manufactured by Wako Pure Chemical Industries, Ltd.) 0.6 g, iodine (JIS reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) 4.5 g was dissolved, 3 g of pyrazine-2,5-dicarboxylic acid dihydrate (manufactured by PolyCarbon Industries), which is a base-forming substance, was added. After stirring at 45 ° C. for 3 hours to complete the reaction, the mixture was dispersed with an ultrasonic disperser for 2 hours. At this time, the hue of the mixed solution changed from brown to dark blue.

  Next, in order to take out the light control particles having a predetermined size from the mixed solution, the light control particles were separated using a centrifuge. The mixture was centrifuged at a speed of 750 G for 10 minutes to remove the precipitate, and further centrifuged at 7390 G for 2 hours to remove the suspended matter and collect the precipitate particles. The precipitate particles were needle-like crystals having a volume average particle diameter of 0.36 μm as measured with a submicron particle analyzer (product name: N4MD, manufactured by Beckman Coulter, Inc.). The precipitate particles were used as light control particles.

(Production example of light control suspension)
45.5 g of the light control particles obtained in the above (Example of manufacturing light control particles) were used as a dispersion medium for the light control suspension butyl acrylate (Wako Special Grade, manufactured by Wako Pure Chemical Industries, Ltd.) / Methacrylic acid. 2,2,2-trifluoroethyl (for industrial use, manufactured by Kyoeisha Chemical Co., Ltd.) / 2-hydroxyethyl acrylate (Wako Grade 1, manufactured by Wako Pure Chemical Industries, Ltd.) copolymer (monomer molar ratio: 18 /1.5/0.5, weight average molecular weight: 2,000, refractive index 1.4719) In addition to 50 g, the mixture was mixed with a stirrer for 30 minutes. Subsequently, isoamyl acetate was removed under reduced pressure at 80 ° C. for 3 hours at a vacuum of 133 Pa using a rotary evaporator to produce a stable liquid light-conditioning suspension free from precipitation and aggregation of light-conditioning particles.

(Example of production of energy ray curable silicone resin)
In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, 17.8 g of both-end silanol polydimethylsiloxane (reagent, manufactured by Chisso Corporation), both-end silanol polydimethyldiphenylsiloxane (reagent, 62.2 g of Chisso Corp.), 20 g of (3-acryloxypropyl) methyldimethoxysilane (reagent, Chisso Corp.), 0.1 g of 2-ethylhexane tin (Wako Pure Chemical Industries Ltd.) The reaction was carried out by refluxing in heptane with an external temperature of 100 ° C. for 3 hours.

Next, 25 g of trimethylethoxysilane (reagent, manufactured by Chisso Co., Ltd.) was added, and the mixture was further refluxed for 2 hours to be dealcoholized, and then heptane was removed under reduced pressure at 80 ° C. for 4 hours at 100 Pa using a rotary evaporator. Thus, an energy ray curable silicone resin having a weight average molecular weight of 35000 and a refractive index of 1.4745 was obtained. ^From the hydrogen integral ratio of ¹ H-NMR, the ethylenically unsaturated bond concentration of this resin was 0.31 mol / kg. The ethylenically unsaturated bond concentration was measured by the following method.

[Measurement method of ethylenically unsaturated bond concentration]
The ethylenically unsaturated bond concentration (mol / kg) was calculated from the hydrogen integral ratio of ¹ H-NMR (integral value of hydrogen of ethylenically unsaturated bond near 6 ppm, integral of phenyl group near hydrogen of 7.5 ppm. Values and integral values around 0.1 ppm of methyl hydrogen). Measurement solvent was CDCl _3. In the resin produced above, the mass ratio calculated from the hydrogen integral ratio of NMR is methyl group: phenyl group: ethylenically unsaturated bond group = 11: 6.4: 1, ethylenically unsaturated bond group in the whole. The ratio of 5.4% was calculated from the respective molecular weights, and the number of ethylenically unsaturated bonding groups per molecule was 9.35. Therefore, the number of moles per kg was calculated to be 0.31 mol / kg.

(Manufacturing example of light control material)
10 g of energy ray curable silicone resin obtained in the above (Example of production of energy ray curable silicone resin), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Ciba Japan ( Co., Ltd.) 0.2 g and dibutyltin dilaurate 0.3 g as an anti-coloring agent were added with 2.5 g of the light control suspension obtained in the above (Production Example of Light Control Suspension). Were mixed together to produce a light-modulating material.

(Production example of transparent conductive resin substrate with primer layer)
Transparent conductive resin made of PET film (300R, manufactured by Toyobo Co., Ltd., thickness 125 μm) coated with ITO (indium tin oxide) transparent conductive film (thickness 30 nm) and having a surface electrical resistance value of 200 to 400Ω AY42-151 (trade name, Toray Dow Corning Co., Ltd.) is 1.0% by mass in a mixed solvent of isopropyl alcohol: 1-methoxy-2-propanol = 1: 1 on the transparent conductive film of the base material. Using a microgravure method (mesh # 150), the entire surface of the solution dissolved in the solution was applied and dried under the conditions of 50 ° C./30 s, 60 ° C./30 s, and 70 ° C./1 min, followed by UV irradiation of 1,000 mJ / The primer layer was formed by photocuring with cm ² (metal halide lamp). AY42-151 contains a photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone). The thickness of the primer layer was 73 nm.

[Measurement method of primer layer thickness]
In addition, the film thickness of the primer layer was measured using the instantaneous spectrophotometer F-20 (made by Filmetrics Co., Ltd.).

(Manufacturing example of light control film)
On the transparent conductive resin base material with the primer layer obtained in (Preparation Example of Transparent Conductive Resin Base Material with Primer Layer), the dimming material obtained in (Preparation Example of Dimming Material) is applied on the entire surface. Thus, a coating layer was formed. Next, the same transparent conductive resin substrate in which the primer layer was similarly formed on the coating layer was laminated and adhered so that the primer layer forming surface was directed to the coating layer of the light control material.
Next, using a metal halide lamp, ultraviolet rays of 3,000 mJ / cm ² were irradiated from the polyester film side of the laminated transparent conductive resin substrate, and the light control suspension was formed into spherical droplets in the ultraviolet cured resin matrix. A dimming film having a thickness of 340 μm was produced in which a dimming layer having a thickness of 90 μm dispersed and formed was sandwiched between two transparent conductive resin substrates.

<Example 1>
The light control film obtained in the above (Manufacturing example of light control film) is cut into 60 mm × 100 mm, and sandwiched between two sheets of flat glass (FL2, manufactured by Nippon Sheet Glass Co., Ltd.) to form a laminate. did. As shown in FIG. 4, there is no gap between the side surfaces (ends) of the laminate using Superbutyl Tape 9230 (manufactured by Sliontec Co., Ltd., base material: polyethylene net + aluminum foil, adhesive material: butyl rubber system). The test body 1 which is a light control structure was produced.

(Evaluation)
The obtained test specimen 1 was put into a constant temperature and humidity chamber (55 ° C./90%), taken out after a lapse of a predetermined time, and then taken out, and the color loss over time was measured with a haze meter (Nippon Denshoku Industries Co., Ltd. NDH-5000W). It was evaluated by measuring the total light transmittance at.

<Example 2>
Specimen 2 in the same manner as in Example 1 except that the end portion was sealed with Superbutyl tape 9830 (manufactured by Sliontec Co., Ltd., base material: polyester film + aluminum foil, adhesive material: butyl rubber) in Example 1. Were made and evaluated.

<Comparative Example 1>
In Example 1, test piece C1 was prepared in the same manner as in Example 1 except that the end was sealed with Superbutyl Tape 9244 (manufactured by Sliontec Co., Ltd., base material: polyethylene film, adhesive material: butyl rubber). ,evaluated.

<Comparative example 2>
In Example 1, test piece C2 was prepared in the same manner as in Example 1 except that the end was sealed with butyl tape 152C (Teraoka Co., Ltd., base material: PET woven fabric, adhesive material: butyl rubber). ,evaluated.

<Comparative Example 3>
In Example 1, a specimen C3 was prepared in the same manner as in Example 1 except that the end was sealed with butyl tape 418 (manufactured by Teraoka Co., Ltd., base material: polyethylene cloth, adhesive material: acrylic rubber). ,evaluated.

<Comparative example 4>
In Example 1, except that the end was sealed with an OPP tape (manufactured by 3M Co., Ltd., base material: OPP film, adhesive material: acrylic), a specimen C4 was prepared in the same manner as in Example 1, evaluated.

<Comparative Example 5>
In Example 1, a specimen C5 was prepared and evaluated in the same manner as in Example 1 except that the end was not sealed with tape.

<Comparative Example 6>
In Example 1, it evaluated similarly to Example 1 except having used the light control film itself instead of the light control structure.
The above evaluation results are summarized in Table 1.

In Comparative Example 6 with only the light control film, since the total light transmittance is the highest, it can be seen that the color of the light control film is lost over time.
On the other hand, in the dimming structure of this invention, it turns out that the raise of a total light transmittance is suppressed over a long term compared with the dimming structure of a comparative example.

DESCRIPTION OF SYMBOLS 1 Light control layer 2 Resin matrix 3 Droplet 4 Transparent conductive resin base material 5a Transparent conductive film 5b Transparent resin base material 6 Primer layer 7 Power supply 8 Switch 9 Dispersion medium 10 Light adjustment particle 11 Incident light 20, 30 Light control structure Body 22 Sealing tape 24 Transparent body 25 Transparent conductive resin substrate 26 Primer layer 27 Droplet 28 Resin matrix

Claims (4)

Two transparent conductive resin substrates;
A light control layer comprising a resin matrix and a light control suspension dispersed in the resin matrix, sandwiched between the two transparent conductive resin substrates;
Two transparent bodies laminated so as to sandwich the transparent conductive resin base material and the light control layer;
A sealing tape that covers a side surface of the laminate including butyl rubber and an inorganic material and having the transparent body, the transparent conductive resin base material, and the light control layer;
A dimmable structure comprising:   The light controllable structure according to claim 1, wherein the transparent body is at least one selected from glass, acrylic resin, polycarbonate resin, vinyl chloride resin, polyester resin, and polyolefin resin.   The dimmable structure according to claim 1, wherein the inorganic material is a metal foil containing aluminum.   The dimming structure according to claim 1, wherein the sealing tape includes a polyethylene net as a tape base material.