JPWO2011093330A1 - Method for producing (meth) acryloyl group-containing polysiloxane resin and light control film using (meth) acryloyl group-containing polysiloxane resin obtained by the method - Google Patents

Abstract

Phosphate ester after the polymerization step of polymerizing a siloxane monomer and / or oligomer containing (meth) acryloyl group and silanol group and a silanol group-containing siloxane monomer and / or oligomer in the presence of a polymerization catalyst and a solvent Is added in a specific amount to deactivate the polymerization catalyst, and the solvent is dissolved at 140 ° C. or lower to obtain a (meth) acryloyl group-containing polysiloxane resin. As a result, in the production of a (meth) acryloyl group-containing polysiloxane resin contained in a resin matrix raw material that is cured to form a resin matrix, the molecular weight of the polysiloxane resin increases in the desolubilization step after polymerization, resulting in a high viscosity. Solves the problem of being unable to be used for optical film coating.

Description

  The present invention relates to a method for producing a (meth) acryloyl group-containing polysiloxane resin used for a light control film having a light control function, and a light control film using the (meth) acryloyl group-containing polysiloxane resin obtained by the method.

  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

  The polysiloxane resin contained in the resin matrix raw material that is cured and becomes a resin matrix used in Patent Document 10 is considered preferable from the viewpoints of ease of synthesis, light control performance, and durability. The polysiloxane resin needs to be dissolved after polymerization to remove the reaction solvent, but the polymerization catalyst for producing the polysiloxane resin has not been deactivated in the process of heating and desolubilizing, and the molecular weight during desorption As a result of studies by the present inventors, it has been found that there is a problem that the viscosity increases and becomes high viscosity and cannot be used for coating of the light control film.

  The present invention provides a polysiloxane resin useful as a component of a resin matrix raw material for a light control film, and provides a polysiloxane resin in which an increase in molecular weight is suppressed, and the molecular weight produced by this method is controlled. An object of the present invention is to provide a light control film using a polysiloxane resin.

  As a result of intensive studies in view of the above problems, the present inventors have deactivated the polymerization catalyst by adding a phosphoric acid ester after the polymerization step of the polysiloxane resin, and then desolvated the above problem. I found that it can be solved.

That is, the present invention is as follows.
(1) The resin matrix material of the 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 method for producing a polysiloxane resin contained in
A polymerization step of polymerizing a siloxane monomer and / or oligomer containing a (meth) acryloyl group and a silanol group and a silanol group-containing siloxane monomer and / or oligomer in the presence of a polymerization catalyst and a solvent;
After the polymerization step, a deactivation step of adding a phosphate ester and deactivating the polymerization catalyst;
After the deactivation step, desolvation of the solvent to obtain a (meth) acryloyl group-containing polysiloxane resin,
The addition amount of the phosphoric acid ester is 25 to 150 parts by mass with respect to 100 parts by mass of the polymerization catalyst,
The method for producing a (meth) acryloyl group-containing polysiloxane resin, wherein the temperature of the desorption step is 140 ° C. or lower.

(2) The manufacturing method of the (meth) acryloyl group containing polysiloxane resin as described in said (1) whose said (meth) acryloyl group containing polysiloxane resin is a weight average molecular weight 35,000-60,000.
(3) The alkoxy of the silane compound in which the siloxane monomer and / or oligomer containing the (meth) acryloyl group and silanol group contains at least one (meth) acryloyl group and at least two alkoxy groups in the molecule. A silanol compound in which a group is converted to a silanol 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 as described in said (1) or (2).
(4) The (meth) acryloyl group-containing polysiloxane resin has three types of structural units of dimethylsiloxane, diphenylsiloxane, and 3-acryloxypropylmethylsiloxane. ) A method for producing an acryloyl group-containing polysiloxane resin.

(5) a resin matrix raw material that is cured by irradiation with energy rays;
A light control film having a light control layer made of a light control material containing a light control suspension dispersed in a dispersion medium in a state where the light control particles can flow,
The resin matrix raw material contains a (meth) acryloyl group-containing polysiloxane resin obtained by the method for producing a (meth) acryloyl group-containing polysiloxane resin according to any one of (1) to (4) above. Light film.

The (meth) acryloyl group having an appropriate weight average molecular weight as the polysiloxane resin contained in the resin matrix material constituting the resin matrix of the light control material by the production method of the (meth) acryloyl group-containing polysiloxane resin of the present invention A containing polysiloxane resin can be obtained.
The disclosure of the present application is disclosed in Japanese Patent Application No. 2010-178665 filed on August 9, 2010, Japanese Patent Application No. 2010-14191 filed on January 26, 2010, and Japanese Patent Application No. 2010-14191 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. 2010-281296 filed on Dec. 17, 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.

<The manufacturing method of the (meth) acryloyl group containing polysiloxane resin of this invention>
The method for producing a (meth) acryloyl group-containing polysiloxane resin according to the present invention includes a resin matrix raw material that is cured by irradiation with energy rays, and a light control suspension dispersed in a dispersion medium so that the light control particles can flow. A process for producing a polysiloxane resin contained in the resin matrix raw material of the light control material comprising:
A polymerization step of polymerizing a siloxane monomer and / or oligomer containing a (meth) acryloyl group and a silanol group and a silanol group-containing siloxane monomer and / or oligomer in the presence of a polymerization catalyst and a solvent;
After the polymerization step, a deactivation step of adding a phosphate ester and deactivating the polymerization catalyst;
After the deactivation step, desolvation of the solvent to obtain a (meth) acryloyl group-containing polysiloxane resin,
The addition amount of the phosphoric acid ester is 25 to 150 parts by mass with respect to 100 parts by mass of the polymerization catalyst,
The temperature of the demelting step is 140 ° C. or less.

  In the present invention, in the method for producing a (meth) acryloyl group-containing polysiloxane resin, the polymerization catalyst for polysiloxane resin is deactivated by phosphoric acid ester, and then desolubilized at 140 ° C. or lower, thereby producing a conventional production method. That is, the problem that the molecular weight increases during the demelting process to increase the viscosity and cannot be used for the application of the light control film is solved.

Hereinafter, the manufacturing method of the (meth) acryloyl group containing polysiloxane resin of this invention is demonstrated for every process.
<1> Polymerization Step The polymerization step of the method for producing the (meth) acryloyl group-containing polysiloxane resin of the present invention comprises a (meth) acryloyl group and a silanol group-containing siloxane monomer and / or oligomer, and a silanol group-containing siloxane system. Monomers and / or oligomers are polymerized in the presence of a polymerization catalyst and a solvent.
In the polymerization step of the method for producing the (meth) acryloyl group-containing polysiloxane resin of the present invention, the raw materials are a siloxane monomer and / or oligomer containing a (meth) acryloyl group and a silanol group, a silanol group-containing siloxane monomer, and From the viewpoint of curing as a resin matrix of the light control layer, it is important that the resulting polysiloxane resin has a crosslinkable substituent, specifically, a (meth) acryloyl group.
Specifically, the alkoxy of the silane compound in which the siloxane monomer and / or oligomer containing the (meth) acryloyl group and silanol group contains at least one (meth) acryloyl group and at least two alkoxy groups in the molecule. A silanol compound obtained by converting a group into a silanol group is preferable.
The silanol group-containing siloxane monomer and / or oligomer used as a raw material for the polysiloxane resin is not particularly limited as long as it is a polysiloxane having silanol groups at both ends. For example, polydimethylsiloxane having silanol groups at both ends ( Hereinafter, also referred to as “both end silanol group-containing polydimethylsiloxane”), polydiphenylsiloxane having silanol groups at both ends (hereinafter also referred to as “both end silanol group-containing polydiphenylsiloxanes”), having both end silanol groups Examples thereof include polymethylphenylsiloxane (hereinafter also referred to as “both terminal silanol group-containing polymethylphenylsiloxane”) and the like, and it is preferable to use two or more thereof.

Commercially available products of polydimethylsiloxane having silanol groups at both ends (both ends silanol group-containing polydimethylsiloxane) are X-21-3114 (manufactured by Shin-Etsu Chemical Co., Ltd.), DMS-S12, DMS-S14 (and above). , Manufactured by Gelest).
As a commercial product of polydiphenylsiloxane having silanol groups at both ends (both ends silanol group-containing polydiphenylsiloxane), PDS-9931 (manufactured by Gelest) and the like can be mentioned.
Examples of commercially available products of polymethylphenylsiloxane having silanol groups at both ends (both ends silanol group-containing polymethylphenylsiloxane) are X-21-3193B (manufactured by Shin-Etsu Chemical Co., Ltd.) and PDS-1615 (manufactured by Gelest). ) And the like.

  As silanol group-containing siloxane monomers and / or oligomers, silanol compounds obtained by hydrolyzing alkoxy groups of dialkoxysilanes such as dimethyl dialkoxysilane and diphenyl dialkoxysilane to form silanol groups, and the silanol compounds are dehydrated. You may use what formed the siloxane bond by condensation reaction and dealcoholization reaction.

  As a siloxane-based monomer and / or oligomer containing a (meth) acryloyl group and a silanol group as a raw material for a polysiloxane resin, an alkoxy group such as (3-acryloxypropyl) methyldimethoxysilane and a (meth) acryloyl group are contained. A silanol group obtained by hydrolyzing an alkoxy group of the siloxane monomer to be hydrolyzed, or a siloxane bond formed by a dehydration condensation reaction may be used.

  A general dehydration catalyst can be used as the polymerization catalyst in the polymerization step. 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 polymerization catalyst include organic tin compounds, metal complexes, basic compounds, and organic phosphorus compounds in addition to the above polymerization catalysts.
Specific examples of the organic tin compound as the polymerization catalyst are not limited to the following examples, but include dibutyltin dilaurate, dibutyltin dioctate, dibutyltin dimaleate, dibutyltin phthalate, dibutyltin diacetate, stannous octylate, dibutyl Tin methoxide, dibutyltin diacetyl acetate, dibutyltin diversate, dibutyltin oxide, dibutyltin monochelate, reaction product of dibutyltin oxide and phthalic acid diester, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctanesan stannous tin And carboxylic acid metal salt polymers such as stannous acetate, dibutyltin maleate polymer, and dimethyltin mercaptopropionate polymer.

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

The basic compound as a polymerization 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 a plurality of nitrogen such as 1,8-diazabicyclo [5.4.0] undec-7-ene Linear or cyclic tertiary amines and quaternary ammonium salts; and the like.

  The organic phosphorus compound as the polymerization 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 polymerization catalysts, organotin compounds are preferably used in the present invention.

  As the solvent used in the polymerization step, heptane, octane or the like can be used.

  Polymerization is carried out at reflux, and the termination of polymerization (dehydration condensation) is carried out when the weight average molecular weight of the reactive product reaches 30,000 to 55,000 while appropriately measuring the molecular weight by gel permeation chromatography (GPC). It is preferable to stop the reaction by lowering the temperature. 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 the polymerization (dehydration condensation), it is also preferable to add a trialkylalkoxysilane such as trimethylmethoxysilane as a reaction terminator for the purpose of endcapping the silanol group end.

<2> Deactivation step After the polymerization step, a phosphoric ester is added to deactivate the polymerization catalyst.

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 the polymerization for obtaining the polysiloxane resin uses a solvent, a desolubilization step is performed after the polymerization reaction.
After synthesizing the (meth) acryloyl group-containing 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. Furthermore, the molecular weight of the polysiloxane resin may increase.
In order to suppress this increase in molecular weight, the polymerization catalyst is deactivated in the present invention. A phosphoric acid ester is used for the deactivation treatment of the polymerization catalyst.
Examples of phosphoric acid esters include acidic phosphoric acid esters, phosphonic acid esters, and alkyl phosphonic acids, and acidic phosphoric acid esters are preferably used.

  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, dibenzyl phosphate and the like.

  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.

  Alkylphosphonic acids include 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, monoiso Decylphosphonic acid, diisodecylphosphonic acid, monoundecylphosphonic acid, diundecylphosphonic acid, monododecylphosphonic acid, didodecylphosphonic acid, monotetradecylphosphonic acid, Examples include tetradecylphosphonic acid, monohexadecylphosphonic acid, dihexadecylphosphonic acid, monooctadecylphosphonic acid, dioctadecylphosphonic acid, monophenylphosphonic acid, diphenylphosphonic acid, monobenzylphosphonic acid, dibenzylphosphonic acid, etc. It is done.

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

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

<3> Desolubilization step After the deactivation step, the solvent during polymerization is desolubilized to obtain a (meth) acryloyl group-containing polysiloxane resin.
In the method for producing a polysiloxane resin of the present invention, it is important that the polymerization catalyst is desolubilized at 140 ° C. or lower after being deactivated with a phosphate ester. 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 the polymerization solvent, 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 and the viscosity tends to increase, which may make it impossible to use 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.

In addition, the (meth) acryloyl group-containing polysiloxane resin obtained after the demelting step of the method for producing the (meth) acryloyl group-containing polysiloxane resin of the present invention has a weight average molecular weight of 35,000 to 60,000. Is preferably 37,000 to 58,000, and more preferably 40,000 to 55,000.
In order to set the weight average molecular weight of the (meth) acryloyl group-containing polysiloxane resin in the above range, the reaction is performed when the molecular weight is measured at 30,000 to 55,000 while measuring the molecular weight with GPC in the polymerization step as described above. Can be stopped.

The (meth) acryloyl group-containing polysiloxane resin obtained by the production method of the present invention preferably contains, for example, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, 3-acryloxypropylmethylsiloxane, etc. as a structural unit. It is preferable to include three types of siloxane, diphenylsiloxane and 3-acryloxypropylmethylsiloxane.
In the (meth) acryloyl group-containing polysiloxane resin, the acrylic unit can control the curability of the light control material, and the refractive index can be controlled by the ratio of the dimethyl unit and the diphenyl unit.

  In order for the (meth) acryloyl group-containing polysiloxane resin to contain, for example, dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, 3-acryloxypropylmethylsiloxane as a structural unit, the above (meth) acryloyl group as a raw material and As a siloxane monomer and / or oligomer containing a silanol group, the methoxy group of (3-acryloxypropyl) methyldimethoxysilane containing at least one acryloyl group and at least two alkoxy groups in the molecule is converted into a silanol group. Silanol group-containing polydimethylsiloxane, both-end silanol group-containing polydiphenylsiloxane, and both ends as the above-mentioned silanol group-containing siloxane monomer and / or oligomer It may be used in two or more selected from the group consisting of silanol-containing polymethylphenylsiloxane.

The (meth) acryloyl group-containing polysiloxane resin obtained by the production method 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. In view of light control performance, durability, etc., it preferably has an alkyl group such as isoamyl group, hexyl group and cyclohexyl group, and an aryl group such as phenyl group and naphthyl group.
In order that the (meth) acryloyl group-containing polysiloxane resin in the present invention has the above substituent, the raw material used for polymerization contains 1 or 2 of the above alkyl group or aryl group in the molecule, and 2 or 3 Obtaining a (meth) acryloyl group-containing polysiloxane resin having an alkyl group or an aryl group by hydrolyzing the alkoxy group of a silane compound containing two alkoxy groups and using the silanol compound converted into a silanol group Can do.
Specific examples of the silane compound containing 1 or 2 alkyl groups and 2 or 3 alkoxy groups in the molecule include diisopropyldimethoxysilane and diisobutyldimethoxysilane. These are available as commercial products. Besides these, several types are available as commercial products.

  Specific examples of the (meth) acryloyl group-containing polysiloxane resin include, for example, resins described in JP-B-53-36515, JP-B-57-52371, JP-B-61-17863, and the like. In order to control the molecular weight of the (meth) acryloyl group-containing polysiloxane resin in the desolubilization step after the polymerization, it is important to produce it by the production method of the present invention.

<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 control material in the present invention includes a resin matrix material that is cured by irradiation with energy rays such as ultraviolet rays, visible rays, and electron beams, and a light control suspension in which the light control particles are dispersed in a dispersion medium in a flowable state. 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.
The resin matrix raw material contains the (meth) acryloyl group-containing polysiloxane resin (A) and the photopolymerization initiator (B) obtained by the production method of the (meth) acryloyl group-containing polysiloxane resin of the present application.
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 250, Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, Irgacure PAG203, Darocure 1173, Darocure MBF, Darocure T65, H Chiba Ji Manufactured by Bread Co., Ltd.), 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, etc. (above, Tokyo Chemical Industry Co., Ltd. Etsu Chemical 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 of the polymer include 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. As the light control particles, for example, there is no affinity for the resin matrix raw material (polymer medium) or the polysiloxane resin in the resin matrix raw material (polymer medium), and the dispersibility of the light control particles can be improved. Pyrazine-2,3-dicarboxylic acid dihydrate, pyrazine-2,5-dicarboxylic acid dihydrate, pyridine-2,5-hydrate, which is a precursor of light control particles in the presence of a molecular dispersant. A polyiodide needle-like crystal produced by reacting one substance selected from the group consisting of dicarboxylic acid and monohydrate with iodine and iodide is 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. And so on. These polyhalides are complex compounds in which a halogen atom reacts with an inorganic substance or an organic substance, and their detailed production methods are disclosed, for example, in US Pat. No. 4,422,963 to Sax.

  As disclosed by Sachs, in the process of synthesizing the light control particles, to form the light control particles of a uniform size, and the dispersibility of the light control particles in the dispersion medium of a specific suspension Therefore, it is preferable to use a polymer substance such as nitrocellulose as the polymer dispersant as described above. 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, the resin used for the resin matrix raw material (polymer medium) is preferably the (meth) acryloyl group-containing polysiloxane resin in the present invention, 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 control 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, the optical correlation method or the dynamic light scattering method, specifically, the long diameter of the light adjusting particle measured by an electron microscope such as the transmission electron microscope described above. It is known to show a good correlation with the short diameter, and is suitable as an index for evaluating the particle diameter.

  The 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 layer is 80% or more, and the transparent conductivity is 3 to 3000 Ω. 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 substrate having a thickness of several nm to 1 μm is formed on a transparent conductive film in order to prevent a short-circuit phenomenon caused by mixing of different substances, etc. A conductive substrate may be used. When the light control film of the present invention is used for a reflection type light control window (for example, a rear view mirror for automobiles), a thin film made of a conductive metal such as aluminum, gold, or silver which is a reflector is used as an electrode. May be used directly.

  In the light control film of the present invention, the light control layer 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 you may be pinched | interposed into two transparent conductive resin base materials of the transparent conductive resin base material which has a primer layer, and the transparent conductive resin base material which does not have a 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 using a die coater method, a comma coater method, a gravure coating method, a micro gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, etc. alone or in combination. 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 or the like after forming the primer layer. 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, for example, known coating means such as a bar coater, applicator, doctor blade, roll coater, die coater, and comma coater can be used.
When the light-modulating material is applied to the surface of the primer layer provided on the transparent conductive resin substrate, or when using a transparent conductive resin substrate 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 the 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 adjusting particles are dispersed in a solvent and a dispersion medium of the light adjusting suspension are mixed, and the solvent is distilled off with a rotary evaporator or the like to prepare a light adjusting suspension.
Next, the light control suspension and the 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 certain thickness, and after removing the solvent contained in the light-modulating material as necessary, it is irradiated with ultraviolet rays 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 rays or the like, the ultraviolet durability shows a stable variable characteristic even after 250 hours have passed, and even when left at -50 ° C. to 90 ° C. for a long time, It is possible to maintain variable characteristics.

  In the production of a light control film using liquid crystal, which is a conventional 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. 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 the product, 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 light shutters, various indoor / outdoor advertisements and signboards, window glass for aircraft / railway vehicles / ships, window glass / back mirror / sunroof for automobiles, glasses, sunglasses, sun visors, etc. Can be used.

As an application method, 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 in 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)
In a four-necked flask equipped with a Dean-Stark trap, condenser, stirrer, and heating device, (3-acryloxypropyl) methyldimethoxysilane (trade name: KBM-5102, manufactured by Shin-Etsu Chemical Co., Ltd.) 10.7 g Then, distilled water 1.4, 0.03 g of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 6.3 g of a mixed solvent of ethanol / methanol = 9/1 by mass ratio were charged, and the temperature was raised to 65 ° C. for 5 hours. Reacted. 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 obtained 10.0g of compounds which converted a part of methoxy group of alkoxysilane into the silanol group. 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.), 10.0 g of the KBM-5102 converted from a methoxy group to a silanol group, 0.01 g of bis (2-ethylhexanoic acid) tin (trade name: KCS-405T, manufactured by Johoku Chemical Industry Co., Ltd.) was charged, and the reaction was performed by refluxing in heptane at 100 ° C. for 5 hours. 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.

(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, the dimming material obtained above is applied over the entire surface, and then the same transparent conductive resin base material in which a primer layer is similarly formed thereon is used. Lamination was made in close contact with the coating layer. 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-adjusting suspension is dispersed and formed in a UV-cured resin matrix as spherical droplets. A 340 μm-thick dimming film having a film-shaped 90 μm-thick dimming layer sandwiched 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 (when no voltage was applied). The light transmittance of the light control film when an AC voltage of 50 Hz of 100 V (effective value) was applied was 46%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as large as 46. It was.

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. The viscosity and weight average molecular weight were 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.

[Viscosity measurement]
Using an E-type viscometer (model: RE-80U, manufactured by Toki Sangyo Co., Ltd.), measurement was performed at a measurement temperature of 25 ° C.
[Weight average molecular weight measurement]
It measured using the following GPC.
Model: L6000 (manufactured by Hitachi, Ltd.)
Detector: L-3300RI (manufactured by Hitachi, Ltd.)
Column: Gelpack (manufactured by Hitachi Chemical Co., Ltd.) GL-R440 + GL-R450 + GL-R400M (three columns are linked)

(Example 2)
Except that 0.005 g of diethyl phosphate (50 parts by mass with respect to 100 parts by mass with respect to the dehydration condensation catalyst bis (2-ethylhexanoic acid) tin) was added, polysiloxane in the same manner as in Example 1. The resin was synthesized to obtain 85.0 g of a (meth) acryloyl group-containing polysiloxane resin (refractive index: 1.4749) having a weight average molecular weight of 46,900 and a viscosity of 11,330 mPa · s.
The light transmittance of the light control film produced using this polysiloxane resin in the same manner as in Example 1 was 1.1% when no AC voltage was applied (when no voltage was applied). In addition, the light transmittance of the light control film when an AC voltage of 100 Hz (effective value) of 50 Hz was applied was 48%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as high as 44, which was good. It was.

(Example 3)
Except that 0.0025 g of diethyl phosphate (25 parts by mass with respect to 100 parts by mass with respect to the dehydration condensation catalyst bis (2-ethylhexanoic acid) tin) was added in the same manner as in Example 1 (meta ) An acryloyl group-containing polysiloxane resin was synthesized to obtain 88.0 g of a polysiloxane resin having a weight average molecular weight of 47,700 and a viscosity of 11,210 mPa · s (refractive index: 1.4747).
The light transmittance of the light control film produced using this polysiloxane resin in the same manner as in Example 1 was 1.1% when no AC voltage was applied (when no voltage was applied). In addition, the light transmittance of the light control film when an AC voltage of 100 Hz (effective value) of 50 Hz was applied was 49%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as large as 45. It was.

Example 4
A polysiloxane resin was synthesized in the same manner as in Example 1 except that the desorption temperature was 130 ° C., and it contained a (meth) acryloyl group having a weight average molecular weight of 46,400 and a viscosity of 11,480 mPa · s. 86.0 g of polysiloxane resin (refractive index 1.4741) was obtained.
The light transmittance of the light control film produced using this polysiloxane resin in the same manner as in Example 1 was 0.9% when no AC voltage was applied (when no AC voltage was applied). Further, the light transmittance of the light control film when an AC voltage of 50 Hz of 100 V (effective value) was applied was 46%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as large as 51, which was good. It was.

(Example 5)
A polysiloxane resin was synthesized in the same manner as in Example 1 except that the desorption temperature was 140 ° C., and it contained a (meth) acryloyl group having a weight average molecular weight of 46,800 and a viscosity of 11,670 mPa · s. 81.0 g of polysiloxane resin (refractive index: 1.4745) was obtained.
The light transmittance of the light control film produced in the same manner as in Example 1 using this polysiloxane resin was 1.0% when no AC voltage was applied (when not applied). In addition, the light transmittance of the light control film when an AC voltage of 100 Hz (effective value) of 50 Hz was applied was 47%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as large as 47, which was good. It was.

(Comparative Example 1)
A polysiloxane resin was synthesized in the same manner as in Example 1 except that desolubilization was performed without adding a phosphate ester, and a (meth) having a weight average molecular weight of 79,000 and a viscosity of 19,900 mPa · s. 88.0 g of acryloyl group-containing polysiloxane resin (refractive index: 1.4753) was obtained. This polysiloxane resin was too viscous to be used for the production of a light control film.

(Comparative Example 2)
A (meth) acryloyl group-containing polysiloxane resin was synthesized in the same manner as in Example 1 except that the demelting temperature was 150 ° C., and the weight average molecular weight was 65,500 and the viscosity was 18,500 mPa · s. 85.6 g of a polysiloxane resin (refractive index: 1.4748) was obtained. This polysiloxane resin was too viscous to be used for the production of a light control film.

(Comparative Example 3)
Except that 0.001 g of diethyl phosphate (10 parts by mass with respect to 100 parts by mass with respect to the dehydration condensation catalyst bis (2-ethylhexanoic acid) tin) was added in the same manner as in Example 1 (meta ) An acryloyl group-containing polysiloxane resin was synthesized to obtain a polysiloxane resin (refractive index: 1.4755) having a weight average molecular weight of 61,300 and a viscosity of 17,900 mPa · s. This polysiloxane resin was too viscous to be used for the production of a light control film.

(Example 6)
In a four-necked flask equipped with a Dean-Stark trap, a condenser, a stirrer, and a heating device, 15.0 g of (3-acryloxypropyl) methyldimethoxysilane (trade name: KBM-5102, manufactured by Shin-Etsu Chemical Co., Ltd.) , 1.9 g of distilled water, 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, heated to 65 ° C. for 5 hours Reacted. 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 14.0g of compounds which converted a part of methoxy group of alkoxysilane into the silanol group. The conversion rate to silanol was 54.5%.
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 both-end silanol group-containing polymethylphenylsiloxane (trade name: X-21-3193B, manufactured by Shin-Etsu Chemical Co., Ltd.), 9.0 g obtained by converting the methoxy group of KBM-5102 to a silanol group, 0.01 g of bis (2-ethylhexanoic acid) tin (trade name: KCS-405T, manufactured by Johoku Chemical Industry Co., Ltd.) was charged, and the reaction was performed by refluxing in heptane at 100 ° 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 polysiloxane resin having a weight average molecular weight of 46,700 and a viscosity of 16,000 (refractive index of 1 .4748) 148.8 g was obtained.

  The light transmittance of the light control film produced using this polysiloxane resin in the same manner as in Example 1 was 0.9% when no AC voltage was applied (when no AC voltage was applied). In addition, the light transmittance of the light control film when an AC voltage of 100 Hz (effective value) of 50 Hz was applied was 47%, and the ratio of the light transmittance when an electric field was applied and when no electric field was applied was as large as 52, which was good. It was.

  By the production method of the present invention, the weight average molecular weight of the (meth) acryloyl group-containing polysiloxane resin contained in the resin matrix raw material constituting the resin matrix can be controlled, and the weight average molecular weight is controlled (meth) acryloyl By using the group-containing polysiloxane resin, a light control film that exhibits a stable light control function can be provided.

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 (5)

Included in the resin matrix raw material of the light control material containing a resin matrix raw material that cures when irradiated with energy rays and a light control suspension dispersed in a dispersion medium in a state where the light control particles can flow A method for producing a polysiloxane resin, comprising:
A polymerization step of polymerizing a siloxane monomer and / or oligomer containing a (meth) acryloyl group and a silanol group and a silanol group-containing siloxane monomer and / or oligomer in the presence of a polymerization catalyst and a solvent;
After the polymerization step, a deactivation step of adding a phosphate ester and deactivating the polymerization catalyst;
After the deactivation step, desolvating the solvent to obtain a (meth) acryloyl group-containing polysiloxane resin,
The addition amount of the phosphoric acid ester is 25 to 150 parts by mass with respect to 100 parts by mass of the polymerization catalyst,
The method for producing a (meth) acryloyl group-containing polysiloxane resin, wherein the temperature in the desolubilization step is 140 ° C. or lower.   The method for producing a (meth) acryloyl group-containing polysiloxane resin according to claim 1, wherein the (meth) acryloyl group-containing polysiloxane resin has a weight average molecular weight of 35,000 to 60,000. The siloxane-based monomer and / or oligomer containing the (meth) acryloyl group and silanol group has the silanol group substituted with the alkoxy group of the silane compound containing at least one (meth) acryloyl group and at least two alkoxy groups in the molecule. A silanol compound converted into a 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. A method for producing a (meth) acryloyl group-containing polysiloxane resin according to claim 1 or 2.   The (meth) acryloyl group-containing polymethacrylate resin according to claim 3, wherein the (meth) acryloyl group-containing polysiloxane resin has three types of structural units of dimethylsiloxane, diphenylsiloxane, and 3-acryloxypropylmethylsiloxane. A method for producing a polysiloxane resin. A resin matrix raw material that cures when irradiated with energy rays;
A light control film having a light control layer made of a light control material containing a light control suspension dispersed in a dispersion medium in a state where the light control particles can flow,
The light control film in which the said resin matrix raw material contains the (meth) acryloyl group containing polysiloxane resin obtained by the manufacturing method of the (meth) acryloyl group containing polysiloxane resin as described in any one of Claims 1-4.

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