JPWO2011093323A1 - Method for producing (meth) acryloyl group-containing polysiloxane resin for light control material, (meth) acryloyl group-containing polysiloxane resin for light control material obtained thereby, light control material and light control film using the same - Google Patents

Abstract

Included in a resin matrix raw material for a light-modulating material containing a resin matrix raw material that cures when irradiated with energy rays, and a light control suspension that is dispersed in a dispersion medium so that the light control particles can flow The manufacturing method of the (meth) acryloyl group containing polysiloxane resin for light control materials shall include the following process: (a) (meth) acryloyl group containing alkoxysilane compound is acid-treated, and (meth) acryloyl group containing silanol compound is obtained. (B) The dehydration condensation of the condensation raw material containing the (meth) acryloyl group-containing silanol compound and the silanol group-containing siloxane monomer and / or oligomer, and (meth) acryloyl group-containing polysiloxane Dehydration condensation process to obtain a resin. Thereby, in the production of the (meth) acryloyl group-containing polysiloxane resin for light control material, the (meth) acryloyl group derived from the condensation raw material can be efficiently introduced into the polysiloxane resin.

Description

  The present invention relates to a method for producing a polysiloxane resin for a light control material used for a light control film having a light control function by applying an electric field, a polysiloxane resin for a light control material obtained thereby, a light control material using the same, and a light control material It relates to an optical film.

  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 film has been proposed (see, for example, Patent Document 10).
In the above method, the resin matrix constituting the light control layer is a resin containing a silicone resin having a substituent having an ethylenically unsaturated bond (hereinafter also referred to as “polysiloxane resin”) and a photopolymerization initiator. It is made of a matrix material (hereinafter also referred to as “polymer medium”), and is cured by irradiation with energy rays such as ultraviolet rays.

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

A polysiloxane resin containing a (meth) acryloyl group is preferably used as a constituent component of a matrix resin raw material that becomes a matrix resin (hereinafter also referred to as “polymer medium”) that is cured by irradiation with energy rays. However, the properties of the light control film are greatly affected by the amount of (meth) acryloyl groups introduced in the polysiloxane resin, and the heat resistance is poor even if the amount of (meth) acryloyl groups introduced is too small or too large. This has been clarified by the study of the present inventors.
In addition, in order to produce a (meth) acryloyl group-containing polysiloxane resin, a (meth) acryloyl group-containing alkoxysilane compound, which is usually used as a condensation raw material, is used as it is in the synthesis, so that the reactivity of the alkoxysilane compound is low, which is good. There is a problem that a necessary amount of (meth) acryloyl groups cannot be introduced into the polysiloxane resin in order to develop excellent heat resistance.

  The present invention provides a method for producing a (meth) acryloyl group-containing polysiloxane resin for a light-modulating material for introducing a necessary amount of (meth) acryloyl group into the polysiloxane resin to exhibit good heat resistance, An object of the present invention is to provide a polysiloxane resin having a controlled (meth) acryloyl group content synthesized by this method, a light control material and a light control film using the same.

  As a result of intensive studies, the present inventors have converted a (meth) acryloyl group-containing alkoxysilane compound into a (meth) acryloyl group-containing silanol compound with an acid or the like, and then dehydrated condensation with a silanol group-containing siloxane monomer and / or oligomer. It has been found that the above problem can be solved by doing so.

That is, the present invention is as follows.
(1) A resin matrix material of a light control material comprising: a resin matrix material that is cured by irradiation with energy rays; and a light conditioning suspension that is dispersed in a dispersion medium so that the light conditioning particles can flow. A method for producing a polysiloxane resin to be used,
The manufacturing method of the (siloxane) group containing polysiloxane resin for light control materials characterized by including the following process (a)-(b).
(A) a silanol conversion step of converting a (meth) acryloyl group-containing alkoxysilane compound into an (meth) acryloyl group-containing silanol compound by acid treatment;
(B) Dehydration condensation step of dehydrating and condensing a condensation raw material containing the (meth) acryloyl group-containing silanol compound and the silanol group-containing siloxane monomer and / or oligomer to obtain a (meth) acryloyl group-containing polysiloxane resin. .

(2) In the (b) dehydrating condensation step, the (meth) acryloyl group-containing silanol compound is 2.0 to 8.0% by mass of the total amount of the condensing raw material. A method for producing a (meth) acryloyl group-containing polysiloxane resin.

(3) The (meth) acryloyl group-containing alkoxysilane compound comprises (3-acryloxypropyl) methyldimethoxysilane, (3-methacryloxypropyl) methyldimethoxysilane, and (3-methacryloxypropyl) methyldiethoxysilane. One or more selected from the group,
The silanol group-containing siloxane monomer and / or oligomer is at least two selected from the group consisting of both-end silanol group-containing polydimethylsiloxane, both-end silanol group-containing polydiphenylsiloxane, and both-end silanol group-containing polymethylphenylsiloxane. The manufacturing method of the (meth) acryloyl group containing polysiloxane resin for light control materials as described in said (1) or (2).

(4) A polysiloxane resin obtained by the production method according to any one of (1) to (3) above, wherein the amount of structural units containing a (meth) acryloyl group is 1 in the total amount of structural units. A (meth) acryloyl group-containing polysiloxane resin for a light-modulating material, which is 3 to 5.0% by mass.

(5) The (meth) acryloyl group-containing polysiloxane resin for a light control material according to the above (4), which has a weight average molecular weight of 35,000 to 60,000.
(6) A resin matrix raw material containing the polysiloxane resin for light modulating material according to (4) or (5) above, a light adjusting suspension dispersed in a dispersion medium in a state where the light adjusting particles can flow, Dimming material containing
(7) The light control film produced using the light control material as described in said (6).

Obtaining a (meth) acryloyl group-containing polysiloxane resin for a light control material suitable for manufacturing a light control film having good heat resistance by the method for manufacturing a (meth) acryloyl group-containing polysiloxane resin for a light control material of the present invention Can do.
The disclosure of the present application is disclosed in Japanese Patent Application No. 2010-281296 filed on December 17, 2010, Japanese Patent Application No. 2010-14191 filed on January 26, 2010, and Japanese Patent Application No. 2010-26191 filed on January 26, 2010. This is related to the subject matter described in Japanese Patent Application No. 2010-14200 and Japanese Patent Application No. 2010-178665 filed on Aug. 9, 2010, the disclosures of which are incorporated herein by reference.

It is a sectional structure schematic diagram of one mode of a light control film of the present invention. It is the schematic for demonstrating the action | operation when the electric field of the light control film of FIG. 1 is not applied. It is the schematic for demonstrating the action | operation when the electric field of the light control film of FIG. 1 is applied. It is the schematic for demonstrating the state of the edge part of a light control film. The light control particles 10 in the droplet 3 are not shown.

A unit containing a (meth) acryloyl group for curing by irradiating energy rays as a constituent of a resin matrix (also referred to as “polymer medium”) raw material used for a light control material of a light control film, and a refractive index The present inventors have found that a polysiloxane resin containing a unit for adjusting the above can be preferably used.
In the present invention, when a synthesis raw material is synthesized so as to include these units, a specific (meth) acryloyl group-containing polysiloxane resin can be efficiently obtained by having a specific step. The present invention relates to a method for producing a (meth) acryloyl group-containing polysiloxane resin for optical materials.

<The manufacturing method of the (meth) acryloyl group containing polysiloxane resin for light control materials of this invention>
The (meth) acryloyl group-containing polysiloxane resin for light control material in the present invention is a resin matrix raw material that is cured by irradiation with energy rays, and a light adjustment suspension dispersed in a dispersion medium in a state where the light adjustment particles can flow. And the production method includes the following steps (a) to (b).
(A) a silanol conversion step of converting a (meth) acryloyl group-containing alkoxysilane compound into an (meth) acryloyl group-containing silanol compound by acid treatment;
(B) Dehydration condensation step of dehydrating and condensing a condensation raw material containing the (meth) acryloyl group-containing silanol compound and the silanol group-containing siloxane monomer and / or oligomer to obtain a (meth) acryloyl group-containing polysiloxane resin. .
Furthermore, in the (b) dehydration condensation step, the (meth) acryloyl group-containing silanol compound is preferably 2.0 to 8.0% by mass of the total amount of the condensation raw materials.

  In the present invention, after the (meth) acryloyl group-containing alkoxysilane compound is converted into a silanol compound with an acid or the like, a condensation raw material containing the silanol compound and the silanol group-containing siloxane monomer and / or oligomer is subjected to dehydration condensation. This solves the problem of the conventional manufacturing method, that is, the problem that the amount of (meth) acryloyl groups necessary for developing good heat resistance cannot be introduced into the polysiloxane resin.

Hereinafter, the manufacturing method of the (meth) acryloyl group containing polysiloxane resin for light control materials of this invention is demonstrated for every process.
<1> Silanol Conversion Step The silanol conversion step in the production method of the present invention is a step of converting a (meth) acryloyl group-containing alkoxysilane compound into a (meth) acryloyl group-containing silanol compound by acid treatment.

The (meth) acryloyl group-containing alkoxysilane compound in the present invention can be a condensation raw material for constituting a unit containing a (meth) acryloyl group for curing by irradiation with energy rays. However, if the polysiloxane resin is used as it is for dehydration condensation, the desired amount cannot be introduced into the polysiloxane resin because the reactivity of alkoxysilane is low. Therefore, in the present invention, after the (meth) acryloyl group-containing alkoxysilane compound is converted to a (meth) acryloyl group-containing silanol compound with an acid or the like, the other condensation raw materials constituting the unit for adjusting the refractive index are dehydrated. Condensation is preferred.
In addition, the other condensation raw material which comprises the unit for adjustment of a refractive index includes a silanol group containing siloxane type monomer and / or an oligomer.

  The (meth) acryloyl group-containing alkoxysilane compound contains a (meth) acryloyl group and an alkoxy group, and after converting the alkoxy group to a silanol group, other condensation raw materials such as a silanol group-containing siloxane monomer and / or oligomer As long as it can form a polysiloxane resin by dehydration condensation. (Meth) acryloxyalkylalkyldialkoxysilane is preferred, and specifically, (3-acryloxypropyl) methyldimethoxysilane, (3-methacryloxypropyl) methyldimethoxysilane, (3-methacryloxypropyl) Methyldiethoxysilane and the like are more preferable, but are not limited thereto.

  Commercially available products of (meth) acryloyl group-containing alkoxysilane compounds include (3-acryloxypropyl) methyldimethoxysilane (KBM-5102), 3-methacryloxypropylmethyldimethoxysilane (KBM-502), and 3-methacryloxypropyl. Examples thereof include methyldiethoxysilane (KBE-502) (manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (Z-6033) (manufactured by Toray Dow Corning Co., Ltd.), and the like.

The conversion ratio of the alkoxy group of the (meth) acryloyl group-containing alkoxysilane compound to the silanol group is determined by the intensity (A) of the peak derived from the hydroxyl group (near 3435 cm ⁻¹ ) and the peak derived from the alkoxy group (2835 cm ⁻ Conversion ratio = A / (A + B) × 100 from the strength (B) in the vicinity of ¹ ). For the synthesis of the polysiloxane resin, the conversion ratio is preferably 40 to 70%, more preferably 45 to 65%. .

In the silanol conversion step, the alkoxy group of the (meth) acryloyl group-containing alkoxysilane compound is converted into a silanol group using an acid. Examples of the acid include organic acids such as acetic acid, formic acid, propionic acid, and p-toluenesulfonic acid.
The amount of the acid used is preferably 0.1 to 5.0% by mass, and preferably 0.1 to 1.0% by mass with respect to the (meth) acryloyl group-containing alkoxysilane compound.
In the silanol conversion step, a solvent may be used, and examples thereof include methanol, ethanol, isopropyl alcohol, etc., but a methanol / ethanol mixed solvent containing distilled water is preferable. The amount of the solvent used is preferably (meth) acryloyl group-containing alkoxysilane compound / mixed solvent = 1 / 0.5 to 1/1, more preferably 1 / 0.7 to 1/1, in terms of mass ratio.
The reaction for silanol conversion is carried out at 63 to 67 ° C. by reacting at a stirring speed of 150 ± 10 rpm for 5 to 6 hours. When the reaction is completed, the reaction solution is cooled to 40 ° C. or lower when the range of 45 to 65% is obtained by the method for measuring the conversion rate to the silanol group.

<2> Dehydration-condensation step The dehydration-condensation step in the production method of the present invention involves dehydrating and condensing a condensation raw material containing the (meth) acryloyl group-containing silanol compound and the silanol group-containing siloxane monomer and / or oligomer, This is a step of obtaining a (meth) acryloyl group-containing polysiloxane resin.
A silanol group-containing siloxane monomer and / or oligomer is used as a condensing raw material together with the (meth) acryloyl group-containing silanol compound obtained by the silanol conversion step.
The silanol group-containing siloxane monomer and / or oligomer serves as a condensing raw material having a unit structure for adjusting the refractive index in the light control film.

The silanol group-containing siloxane monomer is not particularly limited as long as it is a siloxane monomer having a silanol group, and two hydrocarbons such as dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and diisobutyldimethoxysilane. And a silanol compound obtained by hydrolyzing an alkoxy group of a silane compound having a group and two alkoxy groups to form a silanol group.
The silanol group-containing siloxane oligomer is not particularly limited as long as it is a siloxane oligomer containing a silanol group, and after hydrolyzing an alkoxy group of a silane compound such as dimethyl dialkoxysilane or diphenyl dialkoxysilane to form a silanol group. And oligomers in which a siloxane bond is formed by a dehydration condensation reaction. Moreover, the oligomer etc. by which the siloxane bond is formed previously and the both terminal is a silanol group are mentioned. Specifically, both terminal silanol group-containing polydimethylsiloxane, both terminal silanol group-containing polydiphenylsiloxane, both terminal silanol group-containing polymethylphenylsiloxane and the like can be mentioned.

  Examples of commercially available dimethyldimethoxysilane include Z-6329 (Toray Dow Corning), and examples of commercially available diphenyldimethoxysilane include Z-6329 (Toray Dow Corning) and dimethyldimethoxysilane. Commercial products of ethoxysilane such as KBE-22 (Shin-Etsu Chemical Co., Ltd.), commercial products of diisopropyldimethoxysilane, such as Z-6258 (Toray Dow Corning Co., Ltd.), and commercial products of diisobutyldimethoxysilane, such as Z -6275 (Toray Dow Corning Co., Ltd.).

As a commercial item of polydimethylsiloxane containing both terminal silanol groups, X-21-3114 (manufactured by Shin-Etsu Chemical Co., Ltd.), DMS-S12, DMS-S14 (manufactured by Gelest Co., Ltd.) can be mentioned.
PDS-9931 (made by Gelest) etc. are mentioned as a commercial item of both terminal silanol group containing polydiphenylsiloxane.
Examples of commercially available products of both-end silanol group-containing polymethylphenylsiloxanes include X-21-3193B (manufactured by Shin-Etsu Chemical Co., Ltd.), PDS-1615 (manufactured by Gelest) and the like.

(Meth) acryloyl obtained by acid-treating a (meth) acryloyl group-containing alkoxysilane compound such as (3-acryloxypropyl) methyldimethoxysilane in the charging and blending of various condensation raw materials during the production of the polysiloxane resin. The amount of the group-containing silanol compound is important to be 2.0 to 8.0% by mass of the total amount of condensation raw materials of the structural unit of the polysiloxane resin, and preferably 2.3 to 6.9% by mass. .
The condensing raw material includes an end gap agent used for efficiently stopping the reaction. The end gap agent will be described later.
When the amount of the (meth) acryloyl group-containing silanol compound obtained by acid treatment of the (meth) acryloyl group-containing alkoxysilane compound is less than 2.0% by mass, ) The acryloyl group concentration tends to be too lower than the desired concentration, and if it exceeds 8.0% by mass, the (meth) acryloyl group concentration of the resulting polysiloxane resin tends to be too higher than the desired concentration.

  It is obtained by setting the (meth) acryloyl group-containing silanol compound obtained by acid treatment of the (meth) acryloyl group-containing alkoxysilane compound to 2.0 to 8.0% by mass of the total amount of the above condensation raw materials (meta ) A (meth) acryloyl group-containing structural unit of an acryloyl group-containing polysiloxane resin (that is, a (meth) acryloyl group is bonded to a side chain of the Si, with a -Si-O- bond as a structural unit in the main chain of the polysiloxane) The amount of the structural unit is 1.3 to 5.0% by mass, more preferably 1.5 to 4.5% by mass, and the resulting (meth) acryloyl group is contained. The heat resistance of the polysiloxane resin is improved.

  It is preferable to use a dehydration condensation catalyst in the dehydration condensation step. A general dehydration condensation catalyst can be used as the dehydration condensation catalyst. Specific examples thereof include sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and sulfuric acid; sulfonates such as pyridinium p-toluenesulfonate; polyphosphoric acid and the like.

Examples of the dehydration condensation catalyst used in the dehydration condensation process include organic tin compounds, metal complexes, basic compounds, and organic phosphorus compounds in addition to the above catalysts.
Specific examples of the organic tin compound as the dehydration condensation catalyst include, but are not limited to, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin dimaleate, dibutyltin phthalate, dibutyltin diacetate, stannous octylate, Dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide, dibutyltin monochelate, reaction product of dibutyltin oxide and phthalic acid diester, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctanesan first Examples thereof include carboxylic acid metal salt polymers such as tin, stannous acetate, dibutyltin maleate polymer, and dimethyltin mercaptopropionate polymer.

Specific examples of the metal complex as a dehydration condensation catalyst include, but are not limited to, the following examples: lead naphthenate, lead octylate, cobalt naphthenate, iron 2-ethylhexenoate, nickel naphthenate, bismuth octylate, bismuth Carboxylic acid metal salts such as versatate, titanate compounds such as tetrabutyl titanate, tetranonyl titanate, tetraisopropyl titanate, triethanolamine titanate;
Titanate chelates such as bis (acetylacetonyl) dipropyl titanate;
Examples thereof include metal acetylacetonate complexes such as aluminum acetylacetonate complexes and vanadium acetylacetonate complexes.

The basic compound as the dehydration condensation catalyst is not limited to the following examples. For example, aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane;
Quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride;
"DABCO (registered trademark)" series manufactured by Sankyo Air Products Co., Ltd., "DABCO BL" series manufactured by the same company; including multiple nitrogen such as 1,8-diazabicyclo [5.4.0] undec-7-ene Examples thereof include linear or cyclic tertiary amines and quaternary ammonium salts.

  The organic phosphorus compound as the dehydration condensation catalyst is not limited to the following examples, and examples thereof include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate.

  Of these dehydration condensation catalysts, organotin compounds are preferably used in the present invention.

In the dehydration condensation step, a solvent satisfying the following characteristics is usually used, but a solvent such as heptane or octane can be used.
(1) Raw materials and products are dissolved.
(2) The boiling point is higher than the temperature at which the dehydration or dealcoholization reaction proceeds.
(3) The boiling point is low enough to completely remove the solvent after the dehydration condensation step (in the desorption step).

  The dehydration condensation is carried out at reflux, and the dehydration condensation is stopped by appropriately measuring the molecular weight by gel permeation chromatography (GPC) and adjusting the temperature when the weight average molecular weight of the reaction product reaches 30,000 to 55,000. The reaction is preferably stopped by lowering. By stopping the reaction in this manner, the weight average molecular weight of the resulting (meth) acryloyl group-containing polysiloxane resin can be 35,000 to 60,000.

  After dehydration condensation, trialkylalkoxysilane such as trimethylmethoxysilane can be added as an end gap agent for the purpose of end-capping the end of silanol group, adjusting the weight average molecular weight and viscosity of the resulting polysiloxane resin to the desired range. It is preferable because it is possible.

The (meth) acryloyl group-containing polysiloxane resin contained in the resin matrix material of the light control material is preferably used in a solvent-free form. Since dehydration condensation for obtaining a polysiloxane resin uses a solvent, a desolubilization step is performed after the dehydration condensation step.
After the synthesis of the polysiloxane resin, a desorption step is performed to remove the reaction solvent. However, the reaction may not stop sufficiently even if the reaction is stopped by the end cap agent. The weight average molecular weight may increase. In order to suppress this increase in weight average molecular weight, it is preferable to carry out a deactivation treatment of the dehydration condensation catalyst, and it is preferable to use a phosphate ester for the deactivation treatment.
Examples of phosphoric acid esters include acidic phosphoric acid esters, phosphonic acid esters, and alkylphosphonic acids, and it is more preferable to use acidic phosphoric acid esters.

  Specific examples of the acidic phosphate ester are not limited to the following examples, but include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, monopropyl phosphate, dipropyl phosphate, monoisopropyl phosphate, phosphorus Diisopropyl phosphate, monobutyl phosphate, dibutyl phosphate, monopentyl phosphate, dipentyl phosphate, monohexyl phosphate, dihexyl phosphate, monooctyl phosphate, dioctyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate Monodecyl phosphate, didecyl phosphate, monoisodecyl phosphate, diisodecyl phosphate, monoundecyl phosphate, diundecyl phosphate, monododecyl phosphate, didodecyl phosphate, monotetradecyl phosphate, ditetradecyl phosphate, monohexadecyl phosphate, Dihexadecyl phosphate , Phosphoric acid mono-octadecyl, phosphoric acid dioctadecyl phosphate monophenyl, diphenyl phosphate, phosphoric acid mono benzyl, and phosphoric acid dibenzyl is.

  Phosphonic acid esters include monomethyl phosphonate, monoethyl phosphonate, monopropyl phosphonate, monoisopropyl phosphonate, monobutyl phosphonate, monopentyl phosphonate, monohexyl phosphonate, monooctyl phosphonate, monoethylhexyl phosphonate, monodecyl phosphonate Monoisodecyl phosphonate, monoundecyl phosphonate, monododecyl phosphonate, monotetradecyl phosphonate, monohexadecyl phosphonate, monooctadecyl phosphonate, monophenyl phosphonate, monobenzyl phosphonate, and the like.

  Monomethylphosphonic acid, dimethylphosphonic acid, monoethylphosphonic acid, diethylphosphonic acid, monopropylphosphonic acid, dipropylphosphonic acid, monoisopropylphosphonic acid, diisopropylphosphonic acid, monobutylphosphonic acid, dibutylphosphonic acid, monopentylphosphonic acid, Dipentylphosphonic acid, monohexylphosphonic acid, dihexylphosphonic acid, isooctylphosphonic acid, dioctylphosphonic acid, monoethylhexylphosphonic acid, diethylhexylphosphonic acid, monodecylphosphonic acid, didecylphosphonic acid, monoisodecylphosphonic acid, diisodecylphosphonic Acid, monoundecylphosphonic acid, diundecylphosphonic acid, monododecylphosphonic acid, didodecylphosphonic acid, monotetradecylphosphonic acid, ditetradecylphosphonic acid, Hexadecylphosphonic acid, dihexadecylphosphonic acid, monooctadecylphosphonic acid, dioctadecylphosphonic acid and other alkylphosphonic acids, monophenylphosphonic acid, diphenylphosphonic acid, monobenzylphosphonic acid, dibenzylphosphonic acid and other aryl or aralkylphosphonic acids An acid etc. are mentioned.

  The addition amount of the phosphate ester used for the deactivation treatment is preferably 25 to 150 parts by mass, and more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the dehydration condensation catalyst. When the usage-amount of phosphate ester is the said range, the deactivation process of a dehydration condensation catalyst can be performed efficiently.

  The deactivation treatment is usually performed in the range of 70 to 80 ° C. for about 20 minutes.

After the deactivation step, the solvent during dehydration condensation is dissolved to obtain a (meth) acryloyl group-containing polysiloxane resin.
In the method for producing a (meth) acryloyl group-containing polysiloxane resin for a light control material according to the present invention, it is preferable that the dehydration condensation catalyst is deactivated with a phosphoric acid ester and then dissolved at 140 ° C. or lower. When desolubilization exceeds 140 ° C., the molecular weight of the resulting (meth) acryloyl group-containing polysiloxane resin may not be controlled even when the polymerization catalyst is deactivated with a phosphate ester. As a result, the viscosity of the (meth) acryloyl group-containing polysiloxane resin may increase, making it impossible to use the light control film.
Although depending on the type of solvent used in the dehydration condensation step, the preferred desorption temperature is 85 ° C. or higher and 140 ° C. or lower, more preferably 110 ° C. or higher and 120 ° C. or lower. When the temperature is higher than 140 ° C., the molecular weight increases, the viscosity increases, and it cannot be used for the light control film.
In addition, when it cannot desorb at 140 degreeC or less in normal pressure, it is also possible to demelt while reducing pressure.

<(Meth) acryloyl group-containing polysiloxane resin for light control material of the present invention>
The polysiloxane resin for light modulating material of the present invention (hereinafter also specifically referred to as “(meth) acryloyl group-containing polysiloxane resin for light modulating material”) has a structural unit of dimethylsiloxane unit, diphenylsiloxane unit, and (meta ) It is preferably composed of three types of acryloxyalkylmethylsiloxane units, and the (meth) acryloxyalkylmethylsiloxane unit is more preferably a (3-acryloxypropyl) methylsiloxane unit.
The refractive index of the polysiloxane resin can be controlled by the ratio of the dimethyl body and the diphenyl body.

  The amount of the structural unit containing the (meth) acryloyl group in the (meth) acryloyl group-containing polysiloxane resin of the present invention is preferably 1.3 to 5.0% by mass based on the total amount of the structural unit. More preferably, it is -4.5 mass%.

  In order to make the structural unit amount containing the (meth) acryloyl group in the (meth) acryloyl group-containing polysiloxane resin of the present invention 1.3 to 5.0% by mass of the entire structural unit amount, as described above. In the production method of polysiloxane resin, (meth) acryloyl group-containing silanol compound is added to the total amount of polysiloxane resin condensation raw material (silanol group-containing siloxane monomer and / or oligomer, (meth) acryloyl group-containing silanol compound and if necessary The total amount of the end gap agents is 2.0 to 8.0% by mass.

The weight average molecular weight of the (meth) acryloyl group-containing polysiloxane resin of the present invention is preferably 35,000 to 60,000, more preferably 37,000 to 58,000, and 40,000 to 55. Is more preferable.
In order to make the weight average molecular weight of the (meth) acryloyl group-containing polysiloxane resin within the above range, when the molecular weight is measured by GPC in the dehydration condensation process as described above, the molecular weight becomes 30,000 to 55,000. The reaction may be stopped by lowering the temperature.

The (meth) acryloyl group-containing polysiloxane resin of the present invention has, as a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, and a hexyl group. Group, an alkyl group such as a cyclohexyl group, and an aryl group such as a phenyl group and a naphthyl group are preferable in terms of light control performance and durability.
Condensation raw materials for having these substituents include dimethyldimethoxysilane (trade name: Z-6329, manufactured by Toray Dow Corning Co., Ltd.), dimethyldiethoxysilane (trade name: KBE-22, Shin-Etsu Chemical Co., Ltd.) ), Diphenyldimethoxysilane (trade name: Z-6329, manufactured by Toray Dow Corning), diisopropyldimethoxysilane (trade name: Z-6258, manufactured by Toray Dow Corning), diisobutyldimethoxysilane ( Product name: Z-6275, manufactured by Toray Dow Corning Co., Ltd.) Dialkyl dialkoxysilanes, alkylaryl dialkoxysilanes, diaryl dialkoxysilanes and other alkoxy-containing silane compounds, dialkylsiloxane oligomers and terminal silanols Or of an alkoxy group (eg Trade name X-21-3114, manufactured by Shin-Etsu Chemical Co., Ltd.), dialkyldiphenylsiloxane oligomer having terminal silanol or alkoxy group (X-21-3193B, manufactured by Shin-Etsu Chemical Co., Ltd.), n-propyltrimethoxysilane (Trade name: Z-6265, manufactured by Toray Dow Corning Co., Ltd.), n-octylmethoxysiloxane (trade name: Z-6288, manufactured by Toray Dow Corning Co., Ltd.), ethyltrimethoxysilane (trade name: Z -6321, manufactured by Toray Dow Corning Co., Ltd., n-octyltriethoxysilane (trade name: Z-6341, manufactured by Toray Dow Corning Co., Ltd., n-hexyltrimethoxysilane (trade name: Z-6582, Toray Industries, Inc.)・ Dow Corning Co., Ltd.), n-hexyltriethoxysilane (trade name: Z-6586, Toray Dow Corning) Silane compound having three or more alkoxy groups such as cyclohexylmethyldimethoxysilane (trade name: Z-6187, manufactured by Toray Dow Corning Co., Ltd.), and siloxane. , Alkylaryl dialkoxysilane, diaryl dialkoxysilane, the above dialkylsiloxane oligomer, the above dialkyldiphenylsiloxane oligomer, etc. In order to adjust the molecular weight, an end cap agent such as trialkylalkoxysilane is used. Is also possible.

<Light control material and light control film of the present invention>
The light control film of the present invention has two transparent conductive resin substrates and a light control layer sandwiched between the two transparent conductive resin substrates, and the light control layer includes a resin matrix and the above. It consists of a light control material containing the light control suspension dispersed in the resin matrix.

(Light control layer)
The light control layer in the present invention can generally be formed using a light control material. The light-modulating material in the present invention includes a resin matrix raw material that is cured by irradiating energy rays such as ultraviolet rays, visible rays, and electron beams, and a light-regulating suspension dispersed in a dispersion medium in a state where the light-regulating particles can flow. Liquid. It is preferable that the dispersion medium in the light control suspension is capable of phase separation from the resin matrix raw material (polymer medium) and its cured product (resin matrix). It is preferable to use a combination of incompatible or partially compatible resin matrix raw materials (polymer medium) and a dispersion medium.
In addition, a resin matrix raw material contains the (meth) acryloyl group containing polysiloxane resin (A) for photochromic materials of this application, and a photoinitiator (B).
That is, in the light control layer of the light control film of the present invention, the liquid light control suspension is dispersed in the form of fine droplets in the solid resin matrix obtained by curing the resin matrix raw material. The light adjusting particles contained in the light adjusting suspension are preferably rod-shaped or needle-shaped.

  When an electric field is applied to such a light control film, the light adjusting particles having an electric dipole moment suspended and dispersed in the droplets of the light adjusting suspension dispersed in the resin matrix are applied to the electric field. By arranging them parallel to each other, the droplets are converted to a transparent state with respect to the incident light, and the incident light is transmitted with almost no scattering due to a viewing angle or a decrease in transparency.

  It is preferable that the usage-amount of the said photoinitiator (B) is 0.1-20 mass parts with respect to 100 mass parts of said (meth) acryloyl group containing polysiloxane resins (A), 0.2-10. More preferably, it is part by mass.

  As the photopolymerization initiator (B), a photopolymerization initiator that activates radical polymerization when exposed to energy rays can be used.

  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. .

  Commercially available photopolymerization initiators include IRGACURE 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 1300, IRGACURE 819D, IRGACURE 819D, IRGACURE 819D 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE PAG103, IRGACURE PAG108, IRGACURE PAG121, IRGACURE PAG203, DAROCURE 1173, DAROCURE MBF, DAROCURE T65, DAROCURE T65, DAROCURE 42・ Ja C0014, B1225, D1640, D2375, D2963, M1245, B0103, C1105, C0292, E0063, P0211, I0678, P1410, P1377, M1209, F0362, B0139, B1275, B0481, D1621, B1267, B1164 , C0136, C1485, I0591, F0021, A0061, B0050, B0221, B0079, B0222, B1019, B1015, B0942, B0869, B0083, B2380, B2381, D1801, D3358, D2248, D2238, D2253, B1231, M0792, 04 T0157, T2041, T2042, T1188, T1608 (above, manufactured by Tokyo Chemical Industry Co., Ltd.) And the like.

In the present invention, as the dispersion medium in the light-adjusting suspension, one that is phase-separated from the resin matrix raw material (polymer medium) and a resin matrix that is a cured product thereof is used. Preferably, the light adjusting particles serve to disperse the light adjusting particles in a flowable state. Further, the light adjusting particles are selectively attached and coated on the light adjusting particles, and the light adjusting particles are separated during phase separation from the resin matrix raw material (polymer medium). Resin matrix material (polymer medium) that acts to move into phase-separated droplet phase, has no electrical conductivity, has no affinity for resin matrix material (polymer medium), and is used as a light control film A liquid copolymer having a refractive index close to that of the resin matrix formed from the above is used.
As the liquid copolymer, for example, a (meth) acrylic acid ester oligomer having a fluoro group and / or 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 copolymer is used, one monomer unit of either a fluoro group or a hydroxyl group has an affinity for the light control particle, and the remaining monomer unit is a light control suspension in the resin matrix material (polymer medium). Since the liquid works to maintain it stably as droplets, the light adjustment particles are easily dispersed in the light adjustment suspension, and the light adjustment particles are easily induced in the phase-separated droplets during phase separation. .

  Examples of the (meth) acrylic acid ester oligomer having such a fluoro group and / or hydroxyl group include 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, acrylic acid 3 , 5,5-trimethylhexyl / 2-hydroxypropyl acrylate / fumaric acid copolymer, butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl acrylate / acrylic Butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, acrylic acid 1H, 1H, 5H-octafluoropentyl / butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, acrylic acid 1H, 1H, 2H, 2H-hepta Decafluorodecyl / butyl acrylate / 2-hydroxy acrylate Chill copolymer, 2,2,2-trifluoroethyl methacrylate / butyl acrylate / 2-hydroxyethyl acrylate copolymer, 2,2,3,3-tetrafluoropropyl methacrylate / butyl acrylate / acrylic Acid 2-hydroxyethyl copolymer, methacrylic acid 1H, 1H, 5H-octafluoropentyl / butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, methacrylic acid 1H, 1H, 2H, 2H-heptadecafluorodecyl / Butyl acrylate / acrylic acid 2-hydroxyethyl copolymer, butyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, hexyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, octyl methacrylate / 2-methacrylic acid 2- Hydroxyethyl copolymer, decyl methacrylate / 2-hydroxyethyl methacrylate copolymer, undecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, dodecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, tridecyl methacrylate / 2-hydroxyethyl methacrylate copolymer Examples include polymers, tetradecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, hexadecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, octadecyl methacrylate / 2-hydroxyethyl methacrylate copolymer, and the like.

  These (meth) acrylic acid ester oligomers preferably have a standard polystyrene equivalent weight average molecular weight measured by GPC of 1,000 to 20,000, more preferably 2,000 to 10,000.

  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 amount of the fluoro group-containing monomer used exceeds 12 mol%, the refractive index tends to increase and the light transmittance tends to decrease. 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 exceeds 22.0 mol%, there exists a tendency for a refractive index to become large and for light transmittance to fall.

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. Examples of the light control particles include a resin matrix raw material (polymer medium) or a polymer that has no affinity for the polysiloxane resin in the resin matrix raw material (polymer medium) and can improve the dispersibility of the light control particles. Pyrazine-2,3-dicarboxylic acid dihydrate, pyrazine-2,5-dicarboxylic acid dihydrate, pyridine-2,5-dicarboxylic, which is a precursor of light control particles in the presence of a dispersant Polyiodide needle-like crystals produced by reacting one substance selected from the group consisting of acid and monohydrate with iodine and iodide are preferably used. Examples of the polymer dispersant that can be used include nitrocellulose. 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. It is produced by using polyhalides such as. 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, the light control particles of uniform size are formed, and the dispersibility of the light control particles in a specific suspension medium is improved. Therefore, 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 the (meth) acryloyl group-containing polysiloxane resin of the present invention as the resin matrix raw material (polymer medium), and when the (meth) acryloyl group-containing polysiloxane resin is used. Can easily disperse and float in the fine droplets formed by phase separation during the production of the light control film, and as a result, better variable ability can be obtained.

  The particle size of the light preparation particles used in the light control film is preferably the following size from the relationship between the response time with respect to the applied voltage when the light control film is formed 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.

  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, a light correlation method or a dynamic light scattering method, specifically, a major axis of light adjusting particles measured by an electron microscope such as the above-mentioned transmission electron microscope. It is known to show a good correlation with the short diameter, and is suitable as an index for evaluating the particle diameter.

  The light control suspension in the present invention preferably contains 1 to 15% by weight of light control particles, and more preferably 2 to 10% by weight, based on the total weight of the light control suspension. Moreover, it is preferable to contain 30-99 mass% of dispersion media with respect to the total mass of light adjustment suspension, and it is more preferable to contain 50-96 mass%.

  Moreover, it is preferable that a light control material contains 1-100 mass parts of light adjustment suspensions with respect to 100 mass parts of resin matrix raw materials (polymer medium), and it is more preferable to contain 4-70 mass parts. Preferably, 6 to 60 parts by mass is contained, and 8 to 50 parts by mass is particularly preferred.

  In the present invention, the refractive index of the resin matrix material (polymer medium) and the refractive index of the dispersion medium are preferably approximated. Specifically, the difference in refractive index between the resin matrix raw material (polymer medium) and the dispersion medium in the present invention is preferably 0.005 or less, more preferably 0.003 or less.

(Transparent conductive resin substrate)
As a transparent conductive resin base material used when manufacturing a light control film using the light control material according to the present invention, generally, a transparent conductive film (ITO, SnO ₂ , In ₂ O ₃ , a film such as an organic conductive film) is coated, the light transmittance of the transparent resin base material combined with the transparent conductive film is 80% or more, and the surface resistance is 3 to 3000Ω. A resin base material can be used. The light transmittance can be measured according to the total light transmittance measuring method of JIS K7105.

As a transparent resin base material in this invention, 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 films, acrylic resin films, polyether sulfone films, polyarylate films, and polycarbonate films. Although a film is mentioned, 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 to 5,000 nm, and the thickness of the transparent resin substrate is not particularly limited. For example, in the case of a polymer film, 10 to 200 μm is preferable. A transparent resin in which a transparent insulating layer having a thickness of several nanometers to 1 μm is formed on a transparent conductive film in order to prevent a short-circuit phenomenon that occurs due to a narrow interval between transparent resin base materials and mixing of foreign substances. A conductive substrate may be used. When the light control film of the present invention is used for a reflective light control window (for example, a rear view mirror for automobiles), a thin film of conductive metal such as aluminum, gold, or silver as a reflector is used as an electrode. May be used directly.

  The light control film of the present invention is sandwiched between two transparent conductive resin substrates having a primer layer for improving the adhesion between the transparent conductive resin substrate and the light control layer, or the primer layer It may be sandwiched between two transparent conductive resin substrates having a transparent conductive resin substrate having a primer layer and a transparent conductive resin substrate having no primer layer.

  The primer layer includes a material containing a urethane acrylate containing a pentaerythritol skeleton, a material containing a (meth) acrylate having a hydroxyl group in the molecule, a material in which metal oxide fine particles are dispersed in an organic binder resin, The thin film is preferably formed of a phosphate ester having one or more polymerizable groups, a silane coupling agent having an amino group, or the like.

The primer treatment (formation of the primer layer) of the transparent conductive resin substrate in the present invention includes, for example, a material for forming the primer layer, a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, A transparent conductive resin group can be used alone or in combination with a die coater method, 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. This can be done by applying to the material. In addition, when apply | coating, you may dilute with a suitable solvent as needed, and you may use the solution of the material which forms a primer layer. 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 (transparent conductive film side) of the transparent conductive resin base material as necessary, or may be formed on both sides by an impregnation method or a dip coating method. .

  The solvent used for forming the primer layer may be any solvent that dissolves or disperses the material forming the primer layer and can be removed by drying after the primer layer is formed. 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, etc. These solvents can be used.

For application of the light control material to be the light control layer, known coating means such as a bar coater, an applicator, a doctor blade, a roll coater, a die coater, and a 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 that does not have a primer layer on one side, the transparent conductive resin substrate Apply directly. 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 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 order to form a light control film 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, etc. A method of finely dispersing the light control suspension in the matrix raw material (polymer medium), a phase separation method by polymerization of the (meth) acryloyl group-containing polysiloxane resin in the resin matrix raw material (polymer medium), and by solvent volatilization A phase separation method, a phase separation method based on temperature, or the like can be used.

(Light control film)
The light control film of the present invention can be formed using a light control material. The light control material includes a resin matrix formed from a resin matrix raw material (polymer medium) and light dispersed in the resin matrix. It consists of adjustment suspension and forms a light control layer. The light control layer is sandwiched between two transparent conductive resin substrates.

  In order to obtain a light control film, first, a liquid light control suspension is homogeneously mixed with a resin matrix raw material (polymer medium), and the light control suspension is mixed into the resin matrix raw material (polymer medium). A light control material comprising a mixed liquid dispersed in a droplet state is obtained.

Specifically, it is as follows. A liquid in which the light control particles are dispersed in a solvent and a dispersion medium of the light control suspension are mixed, and the solvent is distilled off with a rotary evaporator or the like to prepare a light control suspension.
Next, the light control suspension and the resin matrix raw material (polymer medium) are mixed, and the light control suspension is mixed in a droplet state in the resin matrix raw material (polymer medium) (light control material) To do.

This light-modulating material is applied to a transparent conductive resin substrate with a constant thickness, and if necessary, the solvent contained in the light-modulating material is dried and removed, and then irradiated with ultraviolet light using a high-pressure mercury lamp or the like. The resin matrix raw material (polymer medium) is cured. As a result, a light control layer in which the light control suspension is dispersed in droplets in the cured resin matrix is completed. The light transmittance of the light control layer can be adjusted by variously changing the mixing ratio of the resin matrix material (polymer medium) and the light control suspension. A light control film is obtained by sticking another transparent conductive resin base material on the light control layer formed in this way.
Alternatively, this light-modulating material is applied on the transparent conductive resin substrate at a constant thickness, and if necessary, the solvent contained in the light-modulating material is removed by drying, and then the other transparent conductive resin base After laminating with a material, the resin matrix material (polymer medium) may be cured by irradiating with ultraviolet rays. A light control layer may be formed on both of the two transparent conductive resin 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.

The size (average droplet diameter) of the light control suspension dispersed in the resin matrix is usually 0.5 to 100 μm, preferably 0.5 to 20 μm, more preferably 1 to 5 μm. is there. The size of the droplet is the concentration of each component constituting the light control suspension, the viscosity of the light control suspension and the resin matrix raw material (polymer medium), the resin of the dispersion medium in the light control suspension It is determined by compatibility with the matrix material (polymer medium).
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.

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 light 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 technology, 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 with 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.
In addition, since it is in a film state, there is a problem with the light control glass according to the prior art in which the liquid light adjusting suspension is used as it is, that is, the liquid suspension between the two transparent conductive resin substrates. Difficulty in injecting water, 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 the external environment such as wind pressure, destruction of the sealing material between the transparent conductive resin base materials The leakage of the light control material due to 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 to 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 of the present invention includes, for example, indoor and outdoor partitions, window glass / skylights for buildings, various flat display elements used in the electronics industry and video equipment, various instrument panels, and existing liquid crystal display elements. Suitable for applications such as optical shutters, various indoor / outdoor advertising and information sign boards, window glass for aircraft / railcars / ships, window glass / back mirror / sunroof for automobiles, glasses, sunglasses, sun visors, etc. Can be used.

As an application method, it is possible to directly use the light control film of the present invention. However, depending on the application, for example, the light control film of the present invention may be sandwiched between two base materials or used. It may be used by pasting it on one side. As said base material, glass, the polymer film similar to the said transparent resin base material, etc. can be used, for example.
The structure and operation of the light control film according to the present invention will be described in more detail with reference to the drawings.

  FIG. 1 is a structural schematic diagram of a light control film of one embodiment of the present invention, in which a light control layer 1 is composed of two transparent resin base materials 5b coated with a transparent conductive film 5a. It is sandwiched between four. 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 5 are connected or disconnected. The light control layer 1 includes a film-like resin matrix 2 obtained by UV-curing a resin matrix material (polymer medium) containing the (meth) acryloyl group-containing polysiloxane resin of the present invention, and droplets 3 in the resin matrix 2. It consists of a liquid light conditioning suspension dispersed in form.

  FIG. 2 is a view for explaining the operation of the light control film shown in FIG. 1, and shows a case where the switch 8 is turned off 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. It is scattered or reflected and cannot be transmitted. However, as shown in FIG. 3, when the switch 8 is connected and an electric field is applied, the light adjusting particles 10 are arranged in parallel with the electric field formed by the applied electric field. 10 passes. In this way, a light transmission function without scattering and a decrease in transparency is provided.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

(Production example of light control particles)
A 8.5 mass% iodine isopentyl acetate solution from iodine (JIS reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and isopentyl acetate (reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.), and cellulose nitrate 1/4 LIG An isopentyl acetate solution of 20.0 mass% cellulose nitrate was prepared from (trade name: manufactured by Bergerac NC) and isopentyl acetate. Calcium iodide hydrate (chemical use, manufactured by Wako Pure Chemical Industries, Ltd.) was dried by heating, dehydrated and dissolved in isopentyl acetate to prepare a 20.9 mass% calcium iodide solution.
A 300 ml four-necked flask was equipped with a stirrer and a condenser, 65.6 g of iodine solution and 82.93 g of cellulose nitrate solution were added, and the flask was heated at a water bath temperature of 35 to 40 ° C. After the temperature of the flask contents reached 35 to 40 ° C., 7.41 g of dehydrated methanol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.71 of purified water (produced by Wako Pure Chemical Industries, Ltd.) were added. 525 g was added and stirred. 15.6 g of calcium iodide solution was added, and then 3.70 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 obtained light control particles had a particle diameter of 139 nm determined by particle size distribution measurement, a major axis of 259 nm and an aspect ratio of 4.1 by SEM observation. In addition, after centrifuging the resultant synthesis solution at 9260 G for 5 hours, the supernatant was removed by inclining, and the precipitate remaining at the bottom was added with 5 times the mass of the precipitate, isopentyl acetate to disperse the precipitate with ultrasound, The mass of the whole liquid was measured. The dispersed liquid was weighed on a 1 g metal plate, dried at 120 ° C. for 1 hour, then weighed again to determine the non-volatile content ratio%. From the nonvolatile content ratio and the mass of the entire liquid, the total nonvolatile content, that is, the precipitation yield of 4.15 g was determined.

(Production example of light control suspension)
Using 45.5 g of the light control particles obtained in the above (Production Example of Light Control Particles), butyl acrylate (Wako Special Grade, Wako Pure Chemical Industries, Ltd.) / Methacrylic acid as a dispersion medium for the light control suspension 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 under a vacuum of 133 Pa using a rotary evaporator to produce a stable liquid light-conditioning suspension free of sedimentation and aggregation of light-conditioning particles.

Example 1
(Production example of (meth) acryloyl group-containing polysiloxane resin)
[Silanol conversion process]
In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, (3-acryloxypropyl) methyldimethoxysilane (trade name: KBM-5102, as a (meth) acryloyl group-containing alkoxysilane compound, 15.0 g of Shin-Etsu Chemical Co., Ltd.), 1.9 g of distilled water, 0.04 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. The mixture was heated to 65 ° C. and reacted for 5 hours. After cooling the reaction solution to 40 ° C. or lower, the pressure was reduced to 100 Pa, the temperature was raised to 70 ° C., and a desolubilization step was performed for 2 hours. Then, it cooled to room temperature and obtained 14.0 g of (meth) acryloyl group containing silanol compounds which converted a part of alkoxy group of the alkoxysilane compound into the silanol group. Moreover, the conversion rate to the (meth) acryloyl group containing silanol compound was 54.5%.

[Measurement method of conversion rate to silanol]
The conversion rate of the alkoxysilane compound to the silanol compound is determined from the intensity (A) of the peak derived from the hydroxyl group (near 3435 cm ⁻¹ ) and the intensity (B) of the peak derived from the alkoxy group (near 2835 cm ⁻¹ ) in the infrared spectroscopic measurement. Conversion rate = A / (A + B) × 100.
From infrared spectroscopic measurement after conversion from (3-acryloxypropyl) methyldimethoxysilane to a silanol compound, (A) was Abs = 0.250, and (B) was Abs = 0.221. The conversion rate was calculated as 54.5%.

[Dehydration condensation process]
In a four-necked flask equipped with a Dean-Stark trap, a condenser, a stirrer, and a heating device, 48.0 g of polydimethylsiloxane containing both ends silanol groups (trade name: X-21-3114, manufactured by Shin-Etsu Chemical Co., Ltd.) , 170.0 g of silanol group-containing polymethylphenylsiloxane (trade name: X-21-3193B, manufactured by Shin-Etsu Chemical Co., Ltd.), converting the methoxy group of KBM-5102 into a silanol group in the above [silanol conversion step] 9.0 g of (meth) acryloyl group-containing silanol compound and 0.01 g of bis (2-ethylhexanoic acid) tin (trade name: KCS-405T, manufactured by Johoku Chemical Co., Ltd.) were charged as a condensation raw material, and 100 in heptane The reaction was performed by refluxing at 5 ° C. for 5 hours.
The temperature was cooled to 50 ° C., 109.0 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 100 Pa, the temperature was raised to 115 ° C., desorption was performed for 5 hours, and a (meth) acryloyl group-containing polymer having a weight average molecular weight of 46,700 and a viscosity of 16,000 was obtained. 148.8g of siloxane resin (refractive index 1.4744) was obtained.
At this time, the ratio of the (meth) acryloyl group-containing silanol compound to the polysiloxane resin condensation raw material total amount (including the structural unit raw material siloxane, the (meth) acryloyl group-containing silanol compound and the end gap agent) is 2.7% by mass. there were.
From the NMR hydrogen integration ratio, the amount of 3-acryloxypropylmethylsiloxane structural unit of the resin was 1.9% by mass. In addition, the structural unit amount concentration containing a (meth) acryloyl group was measured by the following method.

[Method for measuring concentration of structural unit containing (meth) acryloyl group]
The amount of 3-acryloxypropylmethylsiloxane structural unit (the amount of structural unit containing (meth) acryloyl group) was calculated from the hydrogen integral ratio of NMR (integral value around 6 ppm of hydrogen of (meth) acryloyl group, phenyl group The integral value near 7.5 ppm of hydrogen and the integral value near 0.1 ppm of hydrogen of methyl group are used). Measurement solvent was CDCl _3.
In the polysiloxane resin produced by the above, (methyl group derived from ^{1 H} diphenyl siloxane) was calculated from the hydrogen integral ratio of NMR :( from phenyl dimethylsiloxane ^{1 H)} :( 3- acryloxypropyl vinyl methyl siloxane coupled to ^{1 H) = 10.00: 27.89:} 0.61, was. The number of hydrogen contained in each structural unit is 10 for diphenylsiloxane, 6 for dimethylsiloxane, and 3 for hydrogen bonded to the vinyl group of 3-acryloxypropylmethylsiloxane. The amount of roxypropylmethylsiloxane structural unit (the amount of structural unit containing a (meth) acryloyl group) was calculated to be 1.9% by mass.

(Preparation of light control material)
7.0 g of (meth) acryloyl group-containing polysiloxane resin obtained in the above (Production example of (meth) acryloyl group-containing polysiloxane resin), bis (2,4,6-trimethylbenzoyl) phenylphosphine as a photopolymerization initiator 0.2 g of fin oxide (trade name: Irgacure 819, manufactured by Ciba Japan Co., Ltd.) and 3.0 g of the light control suspension obtained in the above (manufacturing example of light control suspension) are added, and the machine is added for 1 minute. Were mixed together to produce a light-modulating material.

(Manufacture of light control film)
On the other hand, a transparent film made of a PET film (300R, manufactured by Toyobo Co., Ltd., thickness 125 μm) having a surface electrical resistance value of 200 to 700Ω coated with a transparent conductive film (thickness 300 mm) of ITO (indium tin oxide). On the conductive resin base material, apply the light-modulating material obtained above on the entire surface, and then apply the same transparent conductive resin base material on it so that the transparent conductive film faces the coating layer of the light-modulating material. Laminated and adhered. Next, using a metal halide lamp, 3000 mJ / cm ² of ultraviolet light is irradiated from the polyester film side of the laminated transparent conductive resin base material, and the light control suspension is dispersed in the UV cured resin matrix as spherical droplets. A 340 μm-thick dimming film having a film-shaped 90 μm-thick dimming layer formed between transparent conductive resin substrates was produced.

Subsequently, the light control layer was removed from the edge part of this light control film, and the transparent conductive film of the edge part was exposed in order to take electricity for voltage application (refer FIG. 4).
The droplet size (average droplet diameter) of the light control suspension in the light control film was 3 μm on average. The light transmittance of the light control film was 1.0% when no AC voltage was applied (not applied: T _off ). Further, the light transmittance (T _on ) of the light control film when an AC voltage of 100 Hz (effective value) of 50 Hz was applied was 49%, and the difference in light transmittance between when an electric field was applied and when no electric field was applied (ΔT = T _on- T _off ) was as large as 48 and was good.

  Furthermore, after storing this light control film at 110 degreeC for 2 hours, the same measurement was performed and heat resistance (%) was calculated | required from following Formula. Heat resistance = (ΔT after heat test) / (ΔT before heat test) × 100. As a result, the heat resistance of the light control film was as good as 95%.

When the light control film edge part (part which the light control layer was removed and the transparent conductive film exposed) was observed visually, the bending of the transparent conductive resin base material toward the central part in the thickness direction of the light control film was It was very small (Figure 4).
In addition, evaluation of the magnitude | size of the droplet of the light control suspension liquid in a light control film and the light transmittance of a light control film was measured as follows.

[Measurement method of droplet size of light control suspension]
An SEM photograph was taken from one surface direction of the light control film, a plurality of arbitrarily selected droplet diameters were measured, and the average value was calculated.

[Measurement method of light 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.

(Example 2)
The charged condensation raw materials were 44.0 g of polydimethylsiloxane having both ends silanol groups (X-21-3114), 156.0 g of polymethylphenylsiloxane having both ends silanol groups (X-21-3193B), Example 1 above. A polysiloxane resin was synthesized in the same manner as in Example 1 except that 22.0 g of the (meth) acryloyl group-containing silanol compound obtained in Step 3 and 168.0 g of trimethylethoxysilane (KBM-31) were used. 188.3 g of (meth) acryloyl group-containing polysiloxane resin (refractive index: 1.4742) having an average molecular weight of 49,000 and a viscosity of 13,000 was obtained.
At this time, the ratio of the (meth) acryloyl group-containing silanol compound to the polysiloxane resin condensation raw material total amount (including the structural unit raw material siloxane, the (meth) acryloyl group-containing silanol compound, and the end gap agent) is 5.6% by mass. there were.
In addition, the amount of 3-acryloxypropylmethylsiloxane structural unit (the amount of structural unit containing a (meth) acryloyl group) in this resin was 3.5% by mass from the hydrogen integral ratio of NMR.
The heat resistance of the light control film produced using this polysiloxane resin was as good as 96%.

(Example 3)
The charged condensation raw materials were 44.0 g of polydimethylsiloxane having both ends silanol groups (X-21-3114), 156.0 g of polymethylphenylsiloxane having both ends silanol groups (X-21-3193B), Example 1 above. A polysiloxane resin was synthesized in the same manner as in Example 1 except that 27.0 g of the (meth) acryloyl group-containing silanol compound obtained in Step 1 and 166.0 g of trimethylethoxysilane (KBM-31) were used. 183.7 g of (meth) acryloyl group-containing polysiloxane resin (refractive index: 1.4745) having an average molecular weight of 48,600 and a viscosity of 11,200 was obtained.
At this time, the ratio of the (meth) acryloyl group-containing silanol compound to the polysiloxane resin condensation raw material total amount (including the structural unit raw material siloxane, the (meth) acryloyl group-containing silanol compound, and the end gap agent) is 6.9% by mass. there were.
In addition, the amount of 3-acryloxypropylmethylsiloxane structural unit (the amount of structural unit containing a (meth) acryloyl group) of this resin was 4.2% by mass from the hydrogen integral ratio of NMR.
The heat resistance of the light control film produced using this polysiloxane resin was as good as 96%.

Example 4
As the charged condensation raw materials, 45.0 g of both-end silanol group-containing polydimethylsiloxane (X-21-3114), 159.0 g of both-end silanol group-containing polymethylphenylsiloxane (X-21-3193B), Example 1 above A polysiloxane resin was synthesized in the same manner as in Example 1 except that 9.0 g of the (meth) acryloyl group-containing silanol compound obtained in Step 1 and 170.0 g of trimethylethoxysilane (KBM-31) were used. 184.4 g of (meth) acryloyl group-containing polysiloxane resin (refractive index: 1.4741) having an average molecular weight of 54,800 and a viscosity of 16,000 was obtained.
At this time, the ratio of the (meth) acryloyl group-containing silanol compound to the polysiloxane resin condensation raw material total amount (including the structural unit raw material siloxane, the (meth) acryloyl group-containing silanol compound, and the end gap agent) is 2.3% by mass. there were.
In addition, the amount of 3-acryloxypropylmethylsiloxane structural unit (the amount of structural unit containing a (meth) acryloyl group) of this resin was 1.6% by mass based on the hydrogen integral ratio of NMR.
The heat resistance of the light control film produced using this polysiloxane resin was as good as 92%.

(Comparative Example 1)
Except that the methoxy group of (3-acryloxypropyl) methyldimethoxysilane (KBM-5102) was not directly converted into a silanol group, but was used as it was in the synthesis as a polysiloxane resin condensation raw material, the same as in Example 1. Thus, a polysiloxane resin (refractive index: 1.4745) was synthesized.
180.5 g of a polysiloxane resin having a 3-acryloxypropylmethylsiloxane structural unit amount (a structural unit amount containing a (meth) acryloyl group) of 0.8% by mass, a weight average molecular weight of 45,000 and a viscosity of 13,500 is obtained. It was.
The heat resistance of the light control film produced using this polysiloxane resin was as bad as 75%.

(Example 5)
(Production example of (meth) acryloyl group-containing polysiloxane resin)
[Silanol conversion process]
In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, (3-acryloxypropyl) methyldimethoxysilane (trade name: KBM-5102, as a (meth) acryloyl group-containing alkoxysilane compound, 10.7 g of Shin-Etsu Chemical Co., Ltd.), 1.43 of distilled water, 0.03 g of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 6.3 g of a mixed solvent of ethanol / methanol = 9/1 by mass ratio. The mixture was heated to 65 ° C. and reacted for 5 hours. After cooling the reaction solution to 40 ° C. or lower, the pressure was reduced to 100 Pa with a water-sealed vacuum pump, the temperature was raised to 70 ° C., and a desolubilization step was performed for 2 hours. Then, it cooled to room temperature and 10.0 g of (meth) acryloyl group containing silanol compounds which converted a part of methoxy group of the alkoxysilane compound into the silanol group were obtained. Moreover, the conversion rate to silanol was 53.1%.

In a four-necked flask equipped with a Dean-Stark trap, a condenser, a stirrer, and a heating device, 21.2 g of polydimethylsiloxane containing both ends silanol groups (trade name: X-21-3114, manufactured by Shin-Etsu Chemical Co., Ltd.) , 75.0 g of silanol group-containing polymethylphenylsiloxane (trade name: X-21-3193B, manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acryloyl group obtained by converting the methoxy group of KBM-5102 into a silanol group Containing 10.0 g of silanol compound, 0.01 g of bis (2-ethylhexanoic acid) tin (trade name: KCS-405T, manufactured by Johoku Chemical Industry Co., Ltd.) as a condensation raw material, refluxed in heptane at 100 ° C. for 5 hours The reaction was performed. When the molecular weight reached 42,300 by GPC measurement, heating was stopped, and when the reaction solution temperature dropped to 50 ° C., trimethylethoxysilane (trade name: KBM-31, manufactured by Shin-Etsu Chemical Co., Ltd.) 0 g was added, and the end cap reaction was performed again by refluxing at 85 ° C. for 2 hours.
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 100 Pa with a water-sealed vacuum pump, the temperature was raised to 110 ° C., desorption was performed for 5 hours, and the weight average molecular weight was 46,700, and the viscosity was 11,610 mPa · s. 90.0 g of (meth) acryloyl group-containing polysiloxane resin (refractive index: 1.4757) was obtained.

At this time, the ratio of the (meth) acryloyl group-containing silanol compound to the polysiloxane resin condensation raw material total amount (including the structural unit raw material siloxane, the (meth) acryloyl group-containing silanol compound, and the end gap agent) is 5.4% by mass. there were.
From the NMR hydrogen integration ratio, the amount of 3-acryloxypropylmethylsiloxane structural unit of this resin was 3.5% by mass.
The heat resistance of the light control film produced using this polysiloxane resin was 94%.

  According to the method for producing a polysiloxane resin for light modulating material of the present invention, a necessary amount of (meth) acryloyl groups can be introduced into the polysiloxane resin, and the weight average molecular weight of the polysiloxane resin can be controlled. Moreover, the light control film produced using it can exhibit the stable light control function.

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 12 The light control layer is removed. Exposed surface 13 of transparent conductive film Conductive wire for applying voltage to transparent conductive film

Claims (7)

A polysiloxane used as a resin matrix material for a light control material, comprising: a resin matrix material that is cured by irradiation with energy rays; and a light control suspension that is dispersed in a dispersion medium so that the light control particles can flow. A resin manufacturing method comprising:
The manufacturing method of the (siloxane) group containing polysiloxane resin for light control materials characterized by including the following process (a)-(b).
(A) a silanol conversion step of converting a (meth) acryloyl group-containing alkoxysilane compound into an (meth) acryloyl group-containing silanol compound by acid treatment;
(B) Dehydration condensation step of dehydrating and condensing a condensation material containing the (meth) acryloyl group-containing silanol compound and a silanol group-containing siloxane monomer and / or oligomer to obtain a (meth) acryloyl group-containing polysiloxane resin. .   2. The (meth) acryloyl for light control material according to claim 1, wherein in the (b) dehydration condensation step, the (meth) acryloyl group-containing silanol compound is 2.0 to 8.0 mass% of the total amount of the condensation raw materials. A method for producing a group-containing polysiloxane resin. The (meth) acryloyl group-containing alkoxysilane compound is selected from the group consisting of (3-acryloxypropyl) methyldimethoxysilane, (3-methacryloxypropyl) methyldimethoxysilane, and (3-methacryloxypropyl) methyldiethoxysilane. One or more
The silanol group-containing siloxane monomer and / or oligomer is at least two selected from the group consisting of both-end silanol group-containing polydimethylsiloxane, both-end silanol group-containing polydiphenylsiloxane, and both-end silanol group-containing polymethylphenylsiloxane. The manufacturing method of the (meth) acryloyl group containing polysiloxane resin for light modulation materials of Claim 1 or 2.   It is a (meth) acryloyl group containing polysiloxane resin obtained by the manufacturing method as described in any one of Claims 1-3, Comprising: The structural unit amount containing a (meth) acryloyl group is 1 of the whole structural unit amount. A (meth) acryloyl group-containing polysiloxane resin for a light-modulating material, which is 3 to 5.0% by mass.   The (meth) acryloyl group-containing polysiloxane resin for light-modulating materials according to claim 4, having a weight average molecular weight of 35,000 to 60,000.   A light control material comprising: a resin matrix raw material comprising the polysiloxane resin for light control material according to claim 4 or 5; and a light control suspension dispersed in a dispersion medium in a state where the light control particles can flow. .   The light control film produced using the light control material of Claim 6.

Images