JP2003096320A - Polymer gel composition, and optical element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer gel composition which is easy to make an area larger, is low-cost, has a large change in light transmission properties (a high contrast ratio) and, simultaneously, durability against light (ultraviolet rays) for a long period of time, and an optical element using the same. SOLUTION: The polymer gel composition comprises a swelling fluid, a stimulus-responsive polymer gel which causes a change in volume by absorbing and liberating the swelling fluid in accordance with a stimulus, and a binder resin which covers at least the stimulus-responsive polymer gel, and has an ultraviolet screening means to screen the ultraviolet rays irradiated on the polymer gel composition. The optical element uses this polymer gel composition. It is preferred that the binder resin contains an ultraviolet screening agent, and an ultraviolet screening layer is provided on at least a part of the outer surface of the polymer gel composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer containing a stimuli-responsive polymer gel which is useful as a material for an optical element such as a display element, a recording element, a light control element and a sensor and which changes in volume in response to a stimulus. The present invention relates to a gel composition and an optical element using the same.

[0002]

2. Description of the Related Art In recent years, research and development of a light control element capable of reversibly controlling the amount of transmitted light in response to changes in the external environment have been actively conducted. Such a light control element is useful, for example, as an energy-saving light control glass, a privacy light control glass, an outdoor advertisement, a guide plate, and the like (optical element) particularly as a display element having a large area.

As such an optical element, Japanese Patent Laid-Open No. 11-
Japanese Patent No. 228850 proposes an optical element using a stimuli-responsive polymer gel, and realizes an element capable of greatly changing the light transmittance by various stimuli such as heat, light, electric current and electric field. It is stated that this optical element can also be used as a light control element.

[0004]

The optical element using the stimuli-responsive polymer gel is capable of responding to various stimuli such as heat, light and electric field, and the polymer gel is covered with the resin material. As a result, it is possible to realize a light control element with a large area change easily and at a low cost and with a large change in light transmittance.
However, when such a light control element is used outdoors, for example, for building materials for construction, it is exposed to light (especially ultraviolet rays) for a long time, and the resin, polymer gel, and liquid parts are discolored. Or, it may cause problems such as yellowing and deterioration of responsiveness of the stimuli-responsive polymer gel, which may cause problems such as visual defects and unsatisfactory dimming performance itself. . Therefore, it has been strongly required that the performance can be maintained for a long period of time. In particular, when using the light control element as a building material for construction, it is important to have the same level of durability as the building, so maintaining performance over a long period of time is important, and improvements are required. There is.

Therefore, it is an object of the present invention to solve the above-mentioned problems in the prior art and achieve the following objects.
That is, it is an object of the present invention to provide a polymer gel composition which can be easily and inexpensively made large in area, has a large change in light transmittance (high contrast ratio), and has long-term durability against light (especially ultraviolet rays). And to provide an optical element using the same.

[0006]

The above problems can be solved by the following means. That is, the present invention provides <1> a swelling liquid, a stimuli-responsive polymer gel that causes a volume change by absorbing and releasing the swelling liquid in response to a stimulus, and a binder that covers at least the stimulus-responsive polymer gel. A polymer gel composition comprising: and a polymer gel composition comprising an ultraviolet shielding means for shielding the ultraviolet light incident on the polymer gel composition.

<2> The polymer gel composition according to <1>, wherein the binder contains an ultraviolet blocking agent as the ultraviolet blocking means.

<3> The polymer gel composition according to <2>, wherein the ultraviolet blocking agent is selected from benzophenone compounds, benzotriazole compounds, and cyanoacrylate compounds. .

<4> The ultraviolet shielding means is characterized in that an ultraviolet shielding layer is provided on at least a part of the outer surface of the polymer gel composition, and the ultraviolet shielding layer is provided.
The polymer gel composition according to any one of 1.

<5> The ultraviolet shielding layer is a polymer resin layer having an ultraviolet shielding function.
4> is a polymer gel composition described in 4>.

<6> The above-mentioned <4>, wherein the ultraviolet-shielding layer is a glass layer having an ultraviolet-shielding function.
The polymer gel composition described in 1.

<7> The above-mentioned <1> to <6>, wherein the stimuli-responsive polymer gel contains a light control material.
The polymer gel composition according to any one of 1.

<8> The light control material is a coloring material and / or a light scattering material, and is contained in the stimuli-responsive polymer gel at a saturated absorption concentration or higher or a saturated scattering concentration or higher. It is the polymer gel composition as described above in <7>.

<9> The polymer gel composition according to any one of <1> to <8>, wherein the binder is a resin.

<10> An optical element comprising the polymer gel composition according to any one of <1> to <9>.

<11> The above-mentioned <10>, wherein the polymer gel composition is sandwiched between a pair of substrates.
The optical element according to 1.

<12> The optical element according to <11>, wherein the pair of base materials are sealed.

<13> The optical element according to <11> or <12>, wherein at least one of the pair of base materials has a light-transmitting property.

<14> The optical element according to any one of <11> to <13>, wherein at least one of the pair of base materials is made of a polymer resin film.

<15> At least one of the pair of base materials is made of glass, and the above <11> to <11>
14> The optical element according to any one of <14>.

<16> At least one of the pair of base materials has light reflectivity, and the above <11> to
The optical element according to <15>.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Although the present invention may be described with reference to the drawings, the same reference numerals may be given to those having the same function throughout the drawings, and the description thereof may be omitted.

(Polymer gel composition) The polymer gel composition of the present invention contains at least a swelling liquid, and a stimuli-responsive polymer gel that causes a volume change by absorbing and releasing the swelling liquid in response to a stimulus. A binder for covering the stimuli-responsive polymer gel, and a UV-shielding unit for shielding UV rays incident on the polymer gel composition.

In the polymer gel composition of the present invention, the binder may be a so-called separating member that covers the stimulus-responsive polymer gel and the swelling liquid, or a so-called holding member that covers the stimulus-responsive polymer gel. (In this case, the holding member is made of a material that is impregnated with the swelling liquid). In the case of the configuration including the isolation member, the function of the stimuli-responsive polymer gel can be improved by holding the stimulus-responsive polymer gel and the swelling liquid in a phase-separated manner. this is,
Since the stimuli-responsive polymer gel particles and the swelling liquid are isolated as minute regions and independently exist, coarsening due to aggregation, which is a problem with conventional stimulus-responsive polymer gel particles, is suppressed, and the response speed is increased. This is because it is possible to prevent problems such as deterioration in repeat stability and the like. Further, in the case of a structure including an isolation member, it is possible to enhance transparency, and in particular,
When the polymer gel composition of the present invention is used in a transmissive optical element, the difference in refractive index between the separating member material and the swelling liquid is 0.
It is preferably not more than 05, more preferably 0.0
It is 1 or less. If this difference in refractive index is large, light may be refracted or scattered at the interface between the separating member material and the swelling liquid, and sufficient transparency may not be obtained. In the case of the configuration including the holding member, the function of the stimulus-responsive polymer gel can be improved by holding the stimulus-responsive polymer gel inside, similarly to the isolation member. Further, since the holding member is impregnated with the swelling liquid, it is possible to avoid the phenomenon that the white turbidity is generated due to the scattering at the interface due to the difference in the refractive index with the swelling liquid as in the separating member. When the polymer gel composition of the present invention has a constitution including a binder, it can not only impart the above-mentioned functions, but also can easily have a large area and can be manufactured at low cost. As such a binder, for example, a resin (binder resin) is used.

The polymer gel composition of the present invention comprises a polymer gel, a swelling liquid, and the binder as described above, and has an ultraviolet shielding means, so that it can easily be made large in area and low in size. It has a large change in light transmittance at a high cost (high contrast ratio) and has long-term durability against light (especially ultraviolet rays). For this reason, while having an extremely excellent function, defects caused by deterioration or discoloration of the stimuli-responsive polymer gel, swelling liquid or binder when used for a long time under more severe conditions are significantly reduced. Therefore, it is possible to develop a wider range of applications such as long-term outdoor applications.

The polymer gel composition of the present invention preferably has the following constitutions (a) and (b) as a means for shielding ultraviolet rays to prevent exposure of ultraviolet rays to at least the polymer gel. it can. In particular, in the constitution (a) below, if a flexible material is used as the binder, it is possible to impart the ultraviolet shielding ability while maintaining the flexibility.
Since it can be easily attached to the installation surface having a curved surface such as outdoors, the range of applications is expanded. Further, in the constitution of (b) below, the ultraviolet shielding layer can be provided directly on the outer surface of the composition by coating or adhesion, so that the manufacturing process is simple and the cost can be reduced. (A) A structure in which an ultraviolet blocking agent is contained in the binder. (B) on at least a part of the outer surface of the polymer gel composition,
A structure provided with an ultraviolet shielding layer. The ultraviolet ray shielding means having the configurations of (a) and (b) above means a function of absorbing or reflecting ultraviolet rays (wavelength of 400 nm or less). In particular, in the case of the structure having the ultraviolet shielding layer (the structure of (b)), the incident light having a wavelength of 400 nm or less is 5% or less, preferably 1% or less, more preferably 0.
It is effective to reduce it to 2% or less.

The configuration of (a) will be described. In the case of the constitution (a), it is possible to easily function as an ultraviolet light shielding means by adding an ultraviolet light shielding agent to the binder and dispersing or dissolving it. The ultraviolet blocking agent can be physically adsorbed in the binder, or can be chemically bound to the binder by a covalent bond or an ionic bond. The UV blocking agent is contained in the binder after being physically adsorbed or chemically bound to prevent the UV blocking agent from being dissolved in the swelling liquid from the binder, and the stimulus responsiveness of the stimuli-responsive polymer gel. Can be prevented. As such an ultraviolet blocking agent, an ultraviolet absorbing agent and an ultraviolet scattering agent (reflecting agent)
And both inorganic and organic materials can be used. Examples of the inorganic material include white powders of titanium oxide, zinc oxide, zirconium oxide, talc, kaolin, calcium carbonate, mica, etc., which block ultraviolet rays by absorption, scattering and reflection. In order to maintain transparency, it is necessary that the particle size of these powders is sufficiently small with respect to the wavelength of visible light, and generally 30 n
Titanium dioxide having a particle size of m or less is preferably used. However, if these white powders are mixed into other materials (for example, a binder or a stimuli-responsive polymer gel material) as metal cations, deterioration and discoloration may be significantly promoted, and sufficient caution is required. As the organic material, a triazine compound,
Examples thereof include benzotriazole-based compounds, benzophenone-based compounds, indole-based compounds, cyanoacrylate-based compounds, salicylic acid-based compounds (these compounds are included in the ultraviolet absorber category). Among these,
Benzophenone compounds, benzotriazole compounds, and cyanoacrylate compounds are suitable. The organic material is particularly preferable because it can be melt-kneaded with the binder or the resin that serves as the base material of the ultraviolet blocking layer, and can impart high transparency as compared with the inorganic material. However, these organic materials often have drawbacks such as a relatively narrow absorption region, a functional limitation, and poor light resistance of themselves, so various organic materials may be used as necessary. It is also preferable to combine or use together with an inorganic material.

The benzophenone-based compound is a compound having one or more oxy groups at the ortho position with respect to the carbonyl group in the benzophenone skeleton, and includes 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone and 2,2. Examples include ', 4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, and derivatives thereof. Examples of the benzotriazole-based compound include (2′-hydrooxyphenyl) benzotriazole and (2′-hydroxy-5 ′).
-Methylphenyl) benzotriazole, (2'-hydroxy-5'-octylphenyl) benzotriazole, (2'-hydroxy-3'-tert-butyl-
5'-methylphenyl) -5-chlorobenzotriazole and its derivatives, and further 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α- Dimethylbenzyl)
Phenyl] -2H-benzotriazole, 2- (3,5
-Di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-
Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3
5-Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole and the like can be exemplified as 2-ethylhexyl-2. Examples thereof include -cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. As a triazine-based compound,
2,4-bis (2,4-dimethylphenyl) -6- (2
-Hydroxy-4-n-octyloxyphenyl) 1,
3,5-triazine, 2- (4,6-diphenyl-1,
3,5-triazin-2-yl) -5-((methyl) oxy) phenol, 2- (4,6-diphenyl-1,
3,5-triazin-2-yl) -5-((hexyl)
Oxy) phenol etc. can be illustrated.

The content of the ultraviolet blocking agent varies depending on the form and type of addition to the binder and the required characteristics, but generally, the addition of the smallest amount within the range satisfying the required characteristics provides high price and high stimulus responsiveness. It is preferable when considering the influence on the molecular gel property, for example, 0.0 with respect to the binder.
A preferable content is about 5 to 10% by weight. Even if it is contained in a large amount exceeding this range, a larger ultraviolet ray shielding effect cannot be obtained, and problems such as a decrease in the strength of the binder and adverse effects on the response characteristics of the stimuli-responsive polymer gel may occur. Not preferable. Further, if this range is smaller, the effect may be insufficient.

The configuration of (b) will be described. In the case of the configuration of (b), by providing an ultraviolet blocking layer on at least a part of the outer surface of the polymer gel composition, it can easily function as an ultraviolet blocking means. Of course, the surface provided with such an ultraviolet shielding layer is used as the outdoor side. Further, in the case where both surfaces are exposed to outdoor light, it is also preferable to provide an ultraviolet shielding layer so as to dry both surfaces or the entire polymer gel composition. Furthermore, when an ultraviolet blocking layer is provided, an ultraviolet blocking agent may or may not be added to the binder, and when used in combination, a higher light resistance can be expected due to the combined action with the ultraviolet blocking layer, which is preferable. Is.

Suitable examples of the ultraviolet shielding layer include a polymer resin layer having a ultraviolet shielding function and a glass layer. The polymer resin layer and the glass layer are formed as a transparent plate-like material, a film or the like containing these materials as main components. Generally, these UV shielding functions are obtained by mixing the above-mentioned UV shielding agent with the material constituting the UV shielding layer or coating the surface of the material constituting the UV shielding layer (resin layer or glass layer). Can be granted. Further, these ultraviolet ray shielding functional layers may also have the functions of a base material and a sealing material described later. Further, the ultraviolet blocking layer may be a film made of an ultraviolet blocking agent obtained by directly coating the above-mentioned ultraviolet blocking agent on the surface of the polymer gel composition.

As the glass, float plate glass, tempered plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, etc. can be used. If the safety is strongly required, the mesh plate glass may be used as a transparent plate.

As the polymer resin, polyolefin resin such as polyethylene and polypropylene, vinyl chloride resin,
Styrene resin, ABS resin, polyvinyl alcohol, acrylic resin, acrylonitrile-styrene resin, vinylidene chloride resin, AAS resin, AES resin, polyurethane resin, polyvinyl butyral resin, poly-4-methylpentene-1 resin, polybutene-1 resin, Vinylidene fluoride resin, vinyl fluoride resin, fluororesin, polycarbonate resin, polyamide resin, acetal resin, polyphenylene oxide resin, polybutylene terephthalate,
Polyester resin such as polyethylene terephthalate,
Examples thereof include resin films made of various resin materials such as polyphenylene sulfide resin, polyimide resin, polysulfone resin, polyether sulfone resin, aromatic polyester resin, and polyarylate resin, and laminated films thereof. In particular, a resin film made of a polyester resin or an acrylic resin is preferable because it is excellent in rigidity, elongation resistance, dimensional stability, impact fracture strength, transparency, and lamination suitability. Among them, polyethylene terephthalate (P
It is preferable to use a resin film made of ET) resin.

The thickness of the ultraviolet shielding layer is 50 nm to 1 mm
Is preferred. If the thickness is less than 50 nm, a sufficient ultraviolet ray shielding function may not be obtained. The thickness is not particularly specified from the viewpoint of the ultraviolet ray shielding function, but if it exceeds 1 mm, it may be disadvantageous in terms of cost and handling property. However, when the ultraviolet shielding layer also serves as a base material and a sealing material described later, the thickness may be 1 mm or more.

Examples of the method of forming the ultraviolet shielding layer include a method of adhering a film-shaped polymer resin or glass having an ultraviolet shielding function to a polymer gel composition, a curing material (polymer) in which an ultraviolet shielding agent is dissolved. It can be formed by a method in which a resin) is coated on the surface of the polymer gel composition in a thin film form, and then the solvent is evaporated and dried, or the composition is cured by light or heat. It is also preferable to provide an adhesive layer between the ultraviolet shielding layer and the outer surface of the polymer gel composition in order to enhance the adhesiveness.

As a method of coating the ultraviolet blocking agent as described above, a dry method such as a vacuum deposition method, an ion plating method, a sputtering method, or a solution in which the ultraviolet blocking agent is dissolved or dispersed in a solvent together with a binder is applied. However, a wet method of drying and curing the solvent can also be applied.

The polymer gel composition of the present invention has the above-mentioned ultraviolet ray shielding means for enhancing the light resistance. For example, an infrared absorbing / reflecting agent is added for further enhancing the light resistance. Infrared absorbing / reflecting means may be provided, or stabilizing means such as addition of an antioxidant, a preservative, a pore-forming agent, and a light stabilizer may be provided. These are by using each functional agent in combination with the above ultraviolet blocker,
Each function can be easily given. Furthermore, as a means for protecting the polymer gel composition, a protective layer, an antifouling layer,
An antistatic layer and an antiwear layer are provided. It is also preferable to provide an evaporation prevention layer as a means for preventing evaporation of the internal liquid. Further, when it is used for display, it is also preferable to provide an antireflection layer or the like as a means for improving the visibility. When each of these means is used in combination with the constitution described as the ultraviolet ray blocking means, it becomes possible to impart durability that can withstand use under severe conditions for a long time.

Hereinafter, the ultraviolet blocking means will be described in detail with reference to the drawings together with an example of the polymer gel composition of the present invention, but the present invention is not limited thereto.

The polymer gel composition, as shown in FIG.
A stimuli-responsive polymer gel 1 and a swelling liquid L (not shown),
And a holding member 2. The stimulus-responsive polymer gel 1 and the swelling liquid L are held by being covered by the holding member 2. Further, as a means for blocking ultraviolet rays, the holding member 2 contains an ultraviolet blocking agent.

In the polymer gel composition shown in FIG. 1,
Although the case where the polymer gel composition is formed into a layer is shown as an example, the polymer gel composition of the present invention can also be formed into an arbitrary shape such as a sphere or a lump.

-Ultraviolet Blocking Means- In the polymer gel composition shown in FIG. 1, the holding member 2 contains an ultraviolet blocking agent as the ultraviolet blocking means, but as shown in FIG. The ultraviolet shielding layer 3 may be provided on at least one surface of the polymer gel composition (1). Further, as shown in FIG. 3, the ultraviolet shielding layer 3 can be provided on both surfaces of the layered polymer gel composition. Alternatively, as shown in FIG. 4, the ultraviolet shielding layer 3 may be provided so as to cover the entire polymer gel. The ultraviolet shielding layer 3 may also have a function as a base material.

On the other hand, as shown in FIG.
The polymer gel composition having one surface provided with a pair of base materials 4
A configuration in which the base material 4 and the ultraviolet ray shielding layer 3 are separately provided by sandwiching the base material can also be preferably implemented. Further, as a configuration in which the base material 4 and the ultraviolet shielding layer 3 are separately provided, as shown in FIG. 6, a polymer gel composition is sandwiched between a pair of base materials 4,
A structure in which the ultraviolet blocking layer 3 is provided on the surface of one base material 4 (the surface opposite to the side in contact with the polymer gel composition) (in this case, the base material 3 is the ultraviolet blocking layer 3 having an ultraviolet and ultraviolet blocking function).
Can also be considered. ) Is mentioned. Furthermore, FIG.
As described above, it is also preferable to seal between the pair of base materials 3 with the sealing material 5 for the purpose of preventing evaporation of the liquid contained in the polymer gel composition. Such a sealing material 5 may play the role of the ultraviolet blocking layer 3.

-Stimulus-Responsive Polymer Gel- The stimuli-responsive polymer gel 1 has pH change, ion concentration change, adsorption / desorption of chemical substances, change of solvent composition, or light, heat,
When a stimulus such as an electric current or an electric field is applied, the liquid is absorbed and released to change the volume (swell and contract). In the present invention, the volume change of the stimuli-responsive polymer gel 1 may be unilateral or reversible. However, when the stimuli-responsive polymer gel 1 is used as an optical element or the like, it is preferably reversible. The following is a stimuli-responsive polymer gel 1 that can be used in the present invention.
A specific example of In the specific example, "()" means
It also indicates that the compounds in parentheses are included.

As the polymer gel 1 which responds to a stimulus by a pH change, an electrolyte polymer gel is preferable, and examples thereof include a cross-linked product of poly (meth) acrylic acid and a salt thereof.
A cross-linked product of a copolymer of (meth) acrylic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester, or a salt thereof,
Cross-linked product of polymaleic acid and its salt, cross-linked product of copolymer of maleic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylate, etc. and its salt, cross-linked product of polyvinyl sulfonic acid And vinyl sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester and other copolymers cross-linked products, polyvinyl benzene sulfonic acid cross-linked products and salts thereof, vinyl benzene sulfonic acid Crosslinked products of copolymers with (meth) acrylamide, hydroxyethyl (meth) acrylate, alkyl (meth) acrylic acid esters and the like, salts thereof, crosslinked products of polyacrylamidealkylsulfonic acid and salts thereof, and acrylamidoalkylsulfonic acid ( (Meth) acrylamide, hydroxy Ethyl (meth) acrylate,
Crosslinked products of copolymers with (meth) acrylic acid alkyl esters and the like, salts thereof, crosslinked products of polydimethylaminopropyl (meth) acrylamide and hydrochlorides thereof, dimethylaminopropyl (meth) acrylamide and (meth) acrylic acid, Crosslinked products of copolymers with (meth) acrylamide, hydroxyethyl (meth) acrylate, (meth) acrylic acid alkyl ester and the like, quaternary compounds and salts thereof, and composites of polydimethylaminopropyl (meth) acrylamide and polyvinyl alcohol Body cross-linked products and their quaternized products and salts, cross-linked products of polyvinyl alcohol and poly (meth) acrylic acid complex and its salts, cross-linked products of carboxyalkyl cellulose salts, and cross-linked products of poly (meth) acrylonitrile. Hydrolyzate and its salt are mentioned. The pH change may be due to an electrode reaction such as electrolysis of the liquid or a redox reaction of a compound to be added, or a redox reaction of a conductive polymer, or addition of a chemical substance that changes the pH. preferable.

As the stimuli-responsive polymer gel 1 that responds to stimuli by a change in ion concentration, the same ionic polymer material as the stimulus-responsive polymer gel by a change in pH can be used. The change in ion concentration is preferably caused by addition of salt or the like, use of ion-exchange resin, or the like.

As the stimuli-responsive polymer gel 1 that responds to stimuli by adsorption and desorption of chemical substances, strong ionic polymer gels are preferable, and examples thereof include crosslinked polyvinyl sulfonic acid and vinyl sulfonic acid and (meth) acrylamide. , Hydroxyethyl (meth) acrylate, crosslinked product of copolymer with (meth) acrylic acid alkyl ester, etc., crosslinked product of polyvinylbenzene sulfonic acid and vinylbenzene sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, Cross-linked products of copolymers with (meth) acrylic acid alkyl ester, etc., cross-linked products of poly (meth) acrylamide alkyl sulfonic acid, and (meth) acrylamide alkyl sulfonic acid and (meth) acrylamide, hydroxyethyl (meth) acrylate, ( Meta)
Examples thereof include crosslinked products of copolymers with alkyl acrylates and the like. Particularly, a polyacrylamide alkyl sulfonic acid type polymer is preferably used. in this case,
As the chemical substance, a surfactant, for example, a cationic surfactant such as an alkylpyridine salt such as n-dodecylpyridinium chloride, an alkylammonium salt, a phenylammonium salt or a phosphonium salt such as tetraphenylphosphonium chloride is used. be able to.

As the stimuli-responsive polymer gel 1 which responds to a stimulus by a change in solvent composition, most polymer gels are generally mentioned, and by using a good solvent and a poor solvent of the polymer gel, swelling and contraction are caused. Can be caused.

As the stimuli-responsive polymer gel 1 which responds to a stimulus by applying an electric current or an electric field, a CT complex (charge transfer complex) of a cationic polymer gel and an electron-accepting compound is preferable, and dimethylaminopropyl (meth). Cross-linked products of amino-substituted (meth) acrylamides such as acrylamide, cross-linked products of amino-substituted alkyl esters of (meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminopropyl acrylate, cross-linked products of polystyrene , Cross-linked products of polyvinyl pyridine, cross-linked products of polyvinyl carbazole, cross-linked products of polydimethylaminostyrene, and the like. Particularly, dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate,
Dialkylaminoalkyl (meth) acrylate-based polymers such as diethylaminopropyl (meth) acrylate are preferred. These are benzoquinone, 7,7,8,8
-It can be used in combination with an electron-accepting compound such as tetracyanoquinodimethane (TCNQ), tetracyanoethylene, chloranil, trinitrobenzene, maleic anhydride or iodine.

The stimuli-responsive polymer gel 1 which responds to stimuli by the application of light is preferably a crosslinked product of a hydrophilic polymer compound having a group which ionically dissociates with light, such as a triarylmethane derivative or a spirobenzopyran derivative.
Examples thereof include crosslinked products of copolymers of vinyl-substituted triarylmethane leuco derivatives and (meth) acrylamide.

As the stimuli-responsive polymer gel 1 which responds to stimuli by application of heat, L having a property of aggregating by a hydrophobic interaction at a certain temperature or more and precipitating from an aqueous solution.
A polymer crosslinked body having a CST (lower critical eutectic temperature) (hereinafter referred to as LCST gel), a polymer crosslinked body having a UCST (upper critical eutectic temperature) (hereinafter referred to as UCST gel), and hydrogen each other. IPN (interpenetrating network structure) of a two-component polymer gel to be bound (hereinafter referred to as IPN gel), a polymer gel having a cohesive side chain such as crystallinity (hereinafter referred to as crystalline gel), and the like are preferable. . Among these, LCST gel utilizing hydrophobic interaction is particularly preferable. The LCST gel contracts at a high temperature, and the UCST gel, the IPN gel, and the crystalline gel conversely swell at a high temperature. Specific examples of the LCST gel compound include [N-isopropylacrylamide such as poly-N-isopropylacrylamide.
Alkyl-substituted (meth) acrylamide] crosslinked product or N-
Alkyl-substituted (meth) acrylamide and (meth) acrylic acid and salts thereof, or a crosslinked product of a copolymer of two or more components such as (meth) acrylamide or an alkyl ester of (meth) acrylic acid, a crosslinked product of polyvinyl methyl ether, Examples thereof include crosslinked products of alkyl-substituted cellulose derivatives such as methyl cellulose, ethyl cellulose and hydroxypropyl cellulose. Among these, poly N-isopropyl (meth) acrylamide is preferable. Specific examples of the UCST gel compound include crosslinked zwitterionic polymers having both anion and cation components in the molecule such as poly [3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]. , A crosslinked polymer of a polymer containing an acetylamide derivative exhibiting keto-enol phase mutation. The latter polymer (gel) containing an acetylamide derivative exhibiting keto-enol phase mutation will be described in detail. It is preferable that (meth) acrylamide is further contained as a copolymerization component. Specific examples of the acetyl acrylamide derivative include N-acetyl acrylamide, N-fluoroacetyl acrylamide, N-propionyl acrylamide, N-butanoyl acrylamide, N-pentanoyl acrylamide, N-hexanoyl acrylamide and N.
-Isobutanoyl acrylamide, N-benzoyl acrylamide, N- (3-fluorobenzoyl) acrylamide, N- (2,3-difluorobenzoyl) acrylamide, N-pyridylcarbonyl acrylamide, N-
Pyrimidyl carbonyl acrylamide, N-acetyl methacrylamide, N-fluoroacetyl methacrylamide, N-propionyl methacrylamide, N-butanoyl methacrylamide, N-pentanoyl methacrylamide, N-hexanoyl methacrylamide, N-isobuta Noyl methacrylamide, N-benzoyl methacrylamide, N- (3-fluorobenzoyl) methacrylamide, N- (2,3-difluorobenzoyl) methacrylamide, N-pyridylcarbonyl methacrylamide, N
-Pyrimidyl carbonyl methacrylamide, N-formyl acrylamide, N-formyl methacrylamide, N
-Acroyl-N'-methylurea, N-acroyl-
N'-ethylurea, N-acroyl-N'-fluoromethylurea, N-acroyl-N'-difluoromethylurea, N-acroyl-N'-trifluoromethylurea, N-metacroyl-N'-methylurea, N-
Metacroyl-N'-ethylurea, N-methacroyl-N'-fluoromethylurea, N-methacroyl-
N'-difluoromethylurea, N-methacryloyl-
N'-trifluoromethylurea, methyl N-acryloylcarbamate, ethyl N-acryloylcarbamate,
N-Acroylcarbamate-n-propyl, N-Acroylcarbamate isopropyl, N-Acroylcarbamate-n-butyl, N-Acroylcarbamate isobutyl, N-Acroylcarbamate-t-butyl,
Fluoromethyl N-acroylcarbamate, difluoromethyl N-acroylcarbamate, trifluoromethyl N-acroylcarbamate, N-acroylcarbamate-2,2,2-trifluoromethyl, N-metacroylcarbamine Methyl acid, ethyl N-metacroylcarbamate, n-propyl N-metacroylcarbamate, isopropyl N-metacroylcarbamate,
N-metacroylcarbamate-n-butyl, N-metacloylcarbamate isobutyl, N-metacroylcarbamate-t-butyl, N-metacroylcarbamate fluoromethyl, N-metacroylcarbamate difluoromethyl, N- Trifluoromethyl metacloylcarbamate, N-metacroylcarbamate-2,2,
2-trifluoromethyl and the like can be mentioned. The specific compound of the IPN gel is an IPN body composed of a crosslinked body of poly (meth) acrylamide and a crosslinked body of poly (meth) acrylic acid, and a partially neutralized body thereof (one in which an acrylic acid unit is partially salified). Examples thereof include an IPN body composed of a crosslinked body of a copolymer having poly (meth) acrylamide as a main component and a crosslinked body of poly (meth) acrylic acid, and a partially neutralized body thereof. More preferably, IPN of a crosslinked product of poly [N-alkyl-substituted alkylamide, a crosslinked product of poly (meth) acrylamide and a crosslinked product of poly (meth) acrylic acid
The body and a partially neutralized body thereof are included. Examples of the crystalline gel include a crosslinked product of a copolymer of a (meth) acrylic acid ester having a long chain alkyl group such as an octyl group, a decyl group, a lauryl group, and a stearyl group and a (meth) acrylic acid, or a salt thereof. To be

The temperature (phase transition temperature) showing the volume change of the stimuli-responsive polymer gel 1 which responds to stimuli by the application of heat is
Various designs are possible depending on the structure and composition of the thermoresponsive polymer gel 1. The preferred phase transition temperature is -30 to 30.
It is selected from the range of 0 ° C, particularly preferably -10 to 2
It is in the range of 00 ° C.

As the stimuli-responsive polymer gel 1 which responds to stimuli by the application of heat, in addition to the specific examples illustrated above, gels showing a plurality of phase transition points according to temperature changes can also be suitably used. Specific examples thereof include an IPN body of a crosslinked body of a polyalkyl-substituted (meth) acrylamide such as polyN-isopropyl (meth) acrylamide and a crosslinked body of poly (meth) acrylic acid. These gels are suitably used because they show two phase transition points of swelling-contraction-swelling with an increase in temperature.

In the stimuli-responsive polymer gel 1 which responds to stimuli by application of heat, it is also preferable to incorporate an ionic functional group into the polymer gel material for the purpose of increasing the volume change. Carboxylic acid as the ionic functional group,
Examples thereof include sulfonic acid, ammonium group and phosphoric acid group. The ionic functional group copolymerizes monomers having these functional groups when preparing a polymer gel, and impregnates the polymer gel after synthesis with the monomer to polymerize to form an IPN (interpenetrating network structure) body, A method of partially converting a functional group in the stimuli-responsive polymer gel by a chemical reaction such as hydrolysis or oxidation can be preferably carried out.

The amount of change in volume of the stimuli-responsive polymer gel 1 is not particularly limited, but is preferably as high as possible, and the volume ratio at swelling and contraction is 3 or more, particularly 5 or more.
The volume change of the stimuli-responsive polymer gel of the present invention may be one-way or reversible, but when used as an optical element such as a light control element or a display element,
It is preferably reversible. The amount of change in volume of the stimulus-responsive polymer gel 1 is not particularly limited, but the higher the amount, the more preferable, and the volume ratio during swelling and contraction is 5 or more, particularly 1.
Those of 0 or more are preferable. Particularly, in the present invention, even when the holding member 2 is provided, a high volume change amount of 5 or more when swollen and contracted can be obtained, and the contrast ratio can be increased.

The form of the stimuli-responsive polymer gel 1 is not particularly limited, but it is particularly preferable to use it in the form of particles in view of the stimulus-responsive property. The form of the particles is not particularly limited, but spheres, ellipsoids, polyhedra, porous bodies,
Fiber-shaped, star-shaped, needle-shaped, hollow and the like can be used.

The stimuli-responsive polymer gel 1 preferably has an average particle size in the dry state of 0.01 μm to 5 mm, and particularly preferably 0.01 μm to 1 mm. When the average particle size is less than 0.01 μm, it becomes difficult to obtain optical characteristics, aggregation is likely to occur, and the handling may be difficult when used. On the other hand, if it exceeds 5 mm, the problem that the response speed becomes slow may occur.

The particles of the stimuli-responsive polymer gel 1 are obtained by a method in which the polymer gel is made into particles by a physical pulverization method or the like, and the polymer before crosslinking is made into particles by a chemical pulverization method or the like and then cross-linked and polymerized. It can be produced by a method of obtaining gel particles or a general particle forming method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or the like. In addition, the polymer before cross-linking is extruded with a nozzle base etc. to form fibers,
It is also possible to produce polymer gel particles by a method of crosslinking this and then pulverizing it, or a method of pulverizing the above-mentioned fibers to make particles and then crosslinking.

Various stabilizers such as an ultraviolet absorber and a light stabilizer can be copolymerized or bonded in the stimuli-responsive polymer gel 1 within the range of not impairing its properties. For example, it is preferable to copolymerize or bond a hindered amine-based or hindered phenol-based compound or a compound having a light stabilizing function. The copolymerization amount or binding amount of these compounds is preferably in the range of 0.01% by weight to 5% by weight based on the stimuli-responsive polymer gel.

For the stimuli-responsive polymer gel 1, when the polymer gel composition of the present invention is used in a display device, a recording device or a light control device, a light control material such as a pigment, a dye or a light scattering material is used. It is preferable to add. Furthermore, a material that absorbs or scatters light other than visible light, that is, an infrared absorbing dye, an infrared absorbing or scattering pigment, an ultraviolet absorbing dye, an ultraviolet absorbing or scattering pigment, or the like is added to the stimuli-responsive polymer gel 1. It can be preferably applied as a material for light. Pigments or light scattering agents are suitable as these light control materials. Further, it is preferable that the light control material is physically or chemically immobilized on the stimuli-responsive polymer gel.

The addition amount of such a light control material is as follows.
At the time of drying or shrinking of the stimuli-responsive polymer gel, it is preferable to add an amount of the saturated absorption concentration or the saturated scattering concentration or more. Here, the saturated absorption (or scattering) concentration or higher indicates a region where the relationship between the light control material concentration and the light absorption amount under a specific optical path length deviates largely from the relationship of the linear line. By adding the dimming material having such a concentration to the stimuli-responsive polymer gel 1, the optical density or the scattering can be changed by the swelling / contraction of the stimulus-responsive polymer gel 1. The concentration of the light control material that is equal to or higher than the saturated absorption concentration or the saturated scattering concentration is generally 3% by mass or more, and it is preferable to add the range of 5% by mass to 95% by mass to the stimuli-responsive polymer gel. Preferably 5
It is in the range of 80% by mass to 80% by mass. If it is less than 3% by mass, the effect of adding the light control material cannot be sufficiently obtained, and
When the content exceeds the mass%, the properties of the stimuli-responsive polymer gel may be deteriorated.

Preferable specific examples of the dyes include, for example, black nigrosine dyes and azo dyes such as red, green, blue, cyan, magenta and yellow color dyes, anthraquinone dyes, indigo dyes and phthalocyanine dyes. Examples thereof include dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, and verinone dyes, and those having a high light absorption coefficient are particularly desirable.
For example, C.I. I. Direct Yellow 1, 8, 11, 1
2, 24, 26, 27, 28, 33, 39, 44, 5
0, 58, 85, 86, 87, 88, 89, 98, 15
7, C.I. I. Acid Yellow 1, 3, 7, 11, 1
7, 19, 23, 25, 29, 38, 44, 79, 12
7, 144, 245, C.I. I. Basic Yellow 1,
2, 11, 34, C.I. I. Food Yellow 4, C.I. I.
Reactive Yellow 37, C.I. I. Solvent Yellow 6, 9, 17, 31, 35, 100, 102, 10
3, 105, C.I. I. Direct Red 1, 2, 4,
9, 11, 13, 17, 20, 23, 24, 28, 3
1, 33, 37, 39, 44, 46, 62, 63, 7
5, 79, 80, 81, 83, 84, 89, 95, 9
9, 113, 197, 201, 218, 220, 22
4, 225, 226, 227, 228, 229, 23
0, 231, C.I. I. Acid Red 1, 6, 8, 9,
13, 14, 18, 26, 27, 35, 37, 42, 5
2, 82, 85, 87, 89, 92, 97, 106, 1
11, 114, 115, 118, 134, 158, 18
6, 249, 254, 289, C.I. I. Basic Red 1, 2, 9, 12, 14, 17, 18, 37, C.I.
I. Hood Red 14, C.I. I. Reactive red 2
3, 180, C.I. I. Solvent Red 5, 16, 1
7, 18, 19, 22, 23, 143, 145, 14
6, 149, 150, 151, 157, 158, C.I.
I. Direct Blue 1, 2, 6, 15, 22, 25,
41, 71, 76, 78, 86, 87, 90, 98, 1
63, 165, 199, 202, C.I. I. Acid Blue 1, 7, 9, 22, 23, 25, 29, 40, 41,
43, 45, 78, 80, 82, 92, 93, 127,
249, C.I. I. Basic Blue 1, 3, 5, 7,
9, 22, 24, 25, 26, 28, 29, C.I. I. Food Blue 2, C.I. I. Solvent blue 22, 63,
78, 83-86, 191, 194, 195, 104,
C. I. Direct Black 2, 7, 19, 22, 2
4, 32, 38, 51, 56, 63, 71, 74, 7
5, 77, 108, 154, 168, 171, C.I. I.
Acid Black 1, 2, 7, 24, 26, 29, 3
1, 44, 48, 50, 52, 94, C.I. I. Basic Black 2, 8, C.I. I. Food black 1, 2,
C. I. Reactive Black 31, C.I. I. Food Violet 2, C.I. I. Solvent violet 31,
33, 37, C.I. I. Solvent Green 24, 25,
C. I. Solvent Brown 3, 9 and the like can be mentioned. These dyes may be used alone or in a mixture to obtain a desired color.

Further, in order to immobilize the dye on the stimuli-responsive polymer gel, the so-called dye which has a structure having a polymerizable group such as unsaturated double bond group or the stimulus-responsive polymer gel can react. Reactive dyes and the like are preferably used. Also,
The preferred concentration of the dye contained in the stimuli-responsive polymer gel is in the range of 3% by weight to 50% by weight, particularly preferably in the range of 5% by weight to 30% by weight. Thus, it is desirable that the dye concentration is at least the saturated absorption concentration in the dry or contracted state of the stimuli-responsive polymer gel. Here, the saturated absorption density or higher refers to a region of high dye density in which the relationship between the dye density and the optical density (or the light absorption amount) under a specific optical path length deviates largely from the linear relationship.

Preferable specific examples of the pigment and the light-scattering material include black pigments such as bronze powder, titanium black, various carbon blacks (channel black, furnace black, etc.), white pigments such as titanium oxide, and metal oxides such as silica. Substance, a light scattering material such as calcium carbonate or metal powder, or a color pigment, for example, a phthalocyanine-based cyan pigment, a benzidine-based yellow pigment, a rhodamine-based magenta pigment, or other anthraquinone-based, azo-based, azo metal Examples thereof include various pigments and light-scattering materials such as complex, phthalocyanine-based, quinacridone-based, perylene-based, indigo-based, isoindolinone-based, quinacridone-based, allylamide-based, and the like. For example, as the yellow pigment, a compound represented by a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, and an allylamide compound is used. More specifically, C.I. I. Pigment Yellow 12, 13, 1
4, 15, 17, 62, 74, 83, 93, 94, 9
5, 109, 110, 111, 128, 129, 14
7, 168 and the like are preferably used. As the magenta pigment, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a lake pigment, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound are used. More specifically, C.I. I. Pigment Red 2, 3, 5, 6,
7, 23, 48; 2, 48; 3, 48; 4, 57; 1,
81; 1, 144, 146, 166, 169, 177,
184, 185, 202, 206, 220, 221, 2
54 is particularly preferred. As the cyan pigment, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, for example, as a pigment, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15; 3, 15:
4,60,62,66 etc. can be used especially suitably. It should be noted that these pigments may be used alone, or may be used in combination to obtain a desired color. The average particle size of the primary particles of the pigment and the light scattering material is preferably 0.001 μm to 1 μm, particularly 0.0
It is preferably 1 μm to 0.5 μm. This is because when the particle size is 0.01 μm or less, the stimuli-responsive polymer gel easily flows out, and when the particle size is 0.5 μm or more, the coloring property may be deteriorated. Also, as a pigment,
A surface-modified product may be used for the purpose of improving dispersibility and stability. Specific examples of this modification method include a method of grafting a polymer material on the surface of the pigment and a method of microencapsulating with a resin. Of these, the method of microencapsulation is particularly preferable.

It is necessary that the light control material is contained in the stimulus-responsive polymer gel 1 and does not flow out from the stimulus-responsive polymer gel 1. For that purpose, the crosslink density of the stimuli-responsive polymer gel is optimized so that the light control material is physically confined in the polymer network. It is preferable to use a dimming material having high interaction, a dimming material whose surface is chemically modified, and the like. Specifically, for example, as a pigment or a light scattering material whose surface is chemically modified, an unsaturated group such as a vinyl group or a group such as an unpaired electron (radical) which chemically bonds to the stimuli-responsive polymer gel 1 is used on the surface. Examples thereof include those introduced and those grafted with a polymer material.

The stimuli-responsive polymer gel 1 containing such a light control material is prepared by uniformly dispersing and mixing the light control material in the polymer before crosslinking, and then crosslinking the polymer or polymer precursor monomer during polymerization. It can be produced by a method of adding a light control material to the composition and polymerizing. When adding a pigment or light-scattering material during polymerization, use a pigment or light-scattering material having a polymerizable group or unpaired electrons (radicals) as described above, and chemically bond to the stimuli-responsive polymer gel. Is also preferably carried out. Further, the light control material is preferably dispersed in the stimuli-responsive polymer gel 1 as uniformly as possible. In particular, it is desirable to use a mechanical kneading method, a stirring method, or a dispersant to uniformly disperse the particles in the polymer. The particles of the stimuli-responsive polymer gel containing the light control material can be synthesized by the same method as the particles of the stimuli-responsive polymer gel described above.

-Swelling liquid L- As the swelling liquid L, water, an electrolyte aqueous solution, alcohol, ketone, ether, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile,
Propylene carbonate, other aromatic organic solvents, aliphatic organic solvents and mixtures thereof can be used.
A dispersion stabilizer, a stabilizer such as an antioxidant or an ultraviolet absorber, an antibacterial agent, an antiseptic agent, etc. may be added to the swelling liquid L. Further, pigments such as various pigments, white pigments and dyes can be added.

The mixing ratio of the stimuli-responsive polymer gel 1 and the swelling liquid L is preferably in the range of 1/2000 to 1/1 (weight-stimulating polymer gel / swelling liquid) by weight. If the weight ratio exceeds 1/2000, physical properties such as mechanical strength of the composition may be deteriorated, and if it is less than 1/1, the response speed of volume change due to stimulus response may decrease.

-Holding member 2-The holding member 2 is used as a matrix material as shown in FIG.
That is, that is, the stimuli-responsive polymer gel 1 is held inside.

As a material (matrix material) for the holding member 2, a polymer gel or polymer solution in which a polymer is three-dimensionally cross-linked is preferable. Particularly preferred is a polymer gel in which a polymer is three-dimensionally crosslinked. In this section, the term “polymer gel” simply means not a stimuli-responsive polymer gel but a polymer gel as a material of the holding member 2.

As the polymer gel, agarose, agaropectin, amylose, sodium alginate, propylene glycol alginate, isolikenan, insulin, ethyl cellulose, ethyl hydroxyethyl cellulose, curdlan, casein, carrageenan, carboxymethyl cellulose, carboxymethyl starch, callose, agar. , Chitin, chitosan, silk fibroin, guar gum, quince seed, crown gall polysaccharide, glycogen, glucomannan, keratan sulfate, keratin protein, collagen, cellulose acetate, gellan gum, schizophyllan, gelatin, elephant palm mannan,
Tunisin, dextran, dermatan sulfate, starch,
Tragacanth gum, nigeran, hyaluronic acid, hydroxyethyl cellulose, hydroxypropyl cellulose,
Polymer gels derived from natural polymers such as pustulan, funoran, degraded xyloglucan, pectin, porphyran, methylcellulose, methylstarch, laminaran, lichenan, lentinan, and locust bean gum; in the case of synthetic polymers, poly (meth) acrylic Almost all polymer gels such as acid and its ester, acrylamide, N-alkyl-substituted acrylamide, polyvinyl alcohol and its derivative, polystyrenesulfonic acid, polyvinylpyridine, polyvinylpyrrolidone, and crosslinked synthetic polymers such as polypropylene oxide are preferably used. it can.

The polymer gel may be an organogel or a hydrogel, but when the stimuli-responsive polymer gel 1 is a hydrogel, the polymer gel forming the holding member 2 is also preferably a hydrogel. When the stimuli-responsive polymer gel 1 is an organogel, the polymer gel forming the holding member 2 is also preferably an organogel. Further, it is desirable that these polymer gels are light transmissive. It is desirable that these polymer gels do not change their properties with respect to the stimulus that the stimuli-responsive polymer gel 1 absorbs and releases the swelling liquid, but it is not necessary that they are completely unchanged.

As the polymer solution, most polymer solutions using a swelling liquid as a solvent can be mentioned. Further, the viscosity of the polymer solution is preferably 1 Pa · s or more in order to prevent the flow of the stimuli-responsive polymer gel inside the polymer gel composition. It is preferable that the polymer solution does not affect the responsiveness of the stimuli-responsive gel, but it may have some effect as long as it does not affect the optical characteristics.

The composition ratio of the material of the holding member 2 and the stimuli-responsive polymer gel 1 is 1/30 to 30/1 [(holding member + swelling liquid) / (stimulus-responsive polymer gel + swelling) by weight ratio. Liquid)] is preferable. If it exceeds this range, desired optical properties and physical strength of the material may not be obtained. The range of 1/10 to 10/1 [(holding member + swelling liquid) / (stimulus-responsive polymer gel + swelling liquid)] is more preferable. Further, the size of the region (drop) formed by the stimuli-responsive polymer gel 1 and the swelling liquid L is preferably 0.5 μm to 5 mm, particularly preferably 1 μm to 2 mm in terms of volume average particle diameter.

The holding member 2 may be replaced by a separating member for covering the stimuli-responsive polymer gel and the swelling liquid in a phase-separated manner. Examples of the material for such a separating member include polyester resins, polycarbonate resins, polyvinyl chloride resins, polyvinylidene fluoride and its different copolymers, polytetrafluoroethylene, polystyrene and its different copolymers, and polymethylmethacrylate. Or its hetero-copolymer, polyamide resin, silicone resin, fluorine resin, polyacetal, polyimide, epoxy resin,
Suitable examples include acrylic and vinyl heat, resin compositions such as ultraviolet and electron beam curable resins, silane sol-gel compositions, and inorganic materials such as ceramics and glass. Among them, the resin composition is particularly preferable. The binder such as the holding member and the separating member described above may have a stabilizer such as a dispersion stabilizer and a light stabilizer, an antioxidant, an antibacterial agent, and an antiseptic agent added to the composition thereof.

Here, one example of the method for producing the polymer gel composition of the present invention will be explained, but the method is not limited to this. In the case of a polymer gel composition in which an ultraviolet blocking agent is contained in the binder (for example, in the case of the polymer gel composition of the embodiment shown in FIG. 1), first, the stimuli-responsive polymer gel is mixed with the binder solution. . By dissolving the UV blocking agent compatible with the binder, the UV blocking agent can be dispersed in the binder to provide the UV blocking function. The polymer gel composition of the present invention can be prepared, for example, by coating the surface of a substrate with this dispersion. Since the granular or crushed stimuli-responsive polymer gel easily aggregates, it is preferable to disperse it uniformly using a dispersant such as a surfactant when mixed with the binder (dispersing step). When the material (holding member or separating member forming material) forming the binder (holding member or separating member) is crosslinkable, it is possible to solidify the binder by subjecting it to a crosslinking treatment to form a solid with shape retention. (Solidification step). The solidified polymer gel composition can be used without a substrate. When a polymer solution is used as the binder (holding member), it is preferable to seal the polymer gel composition between the substrates so that the polymer solution does not flow.

In the case of a polymer composition having a UV blocking layer (for example, the polymer gel composition of the embodiment shown in FIGS. 2, 3 and 4), in the case of containing a UV blocking agent in the binder described above. It can be manufactured by a method similar to. That is, at least a part of the surface of the polymer gel composition prepared without adding an ultraviolet absorber in the binder is coated with an ultraviolet blocking agent, a film having a ultraviolet blocking function (polymer resin), an ultraviolet blocking function. It can be manufactured by using a method such as bonding glass having the above with an appropriate adhesive or the like. It is also preferable to add an ultraviolet absorber in the binder depending on the purpose.

(Optical Element) An optical element (optical element of the present invention) using the polymer gel composition of the present invention will be described below. In the optical element of the present invention, the polymer gel composition of the present invention can be used as it is as an optical element for light control, display and the like. By using the polymer gel composition of the present invention, the optical element of the present invention is particularly suitable as a light control element or a display element for outdoor use. Further, in order to improve strength, durability and function, the composition of the present invention is formed on a substrate in layers, or the composition is sandwiched between a pair of substrates to form an optical element. Can also be Further, in the optical element of the present invention, the polymer gel composition of the present invention can be used by forming it into any shape such as spherical shape, lump shape and the like. It is also preferable to carry out the sealing so as to enclose.

In the optical element of the present invention, the stimulus applied may be a natural stimulus or an artificial stimulus. It is also possible to combine a stimulating means such as heat, light, or electricity. When utilizing natural stimuli such as light and heat, it can be used for a light control element, an optical shutter, a sensor and the like. On the other hand, in the case of utilizing artificial stimulus, by providing means for applying heat, light, electric field or the like from inside or outside of the element, the display element, the recording element, the light modulation element, etc. can be used for the above purposes. It is also possible to apply to other uses. For example, as a stimuli-responsive polymer gel,
When a stimuli-responsive polymer gel that responds to stimuli by applying heat is used, dimming and display can be performed by natural energy such as changes in temperature and changes in the amount of sunlight. It is also possible to actively adjust the light by providing. In this case, the stimulating means is
Those that substantially give heat to the polymer gel or those that absorb heat from the polymer gel, in addition to the energization heating resistor, may be those that cause a change in the amount of heat due to the applied energy, light application, Various means such as application of electromagnetic waves and application of magnetic fields can be used. Among these, it is particularly preferable to use an electric heating resistor, specifically, a metal layer typified by a Ni—Cr alloy, a metal oxide layer such as tantalum boride, tantalum nitride or ITO, or a carbon layer. The heat generating resistance layer is preferable, and the current generating heat generating element can generate heat by passing an electric current through these heat generating resistance elements. Further, it is also preferable that the stimulating means is patterned or segmented to dimming an arbitrary part. It is also preferable to arrange a stimuli-responsive polymer gel having specific characteristics corresponding to these patterns.

As the material of the base material, inorganic materials such as glass and ceramics, various polymer resin films (including plate-shaped ones) and the like are preferably used. The substrate may be composed of a plurality of substrates depending on the configuration of the optical element, but it is preferable that at least the substrate on the display surface side is transparent in view of the properties of the optical element. It is also preferable to use a substrate having light reflectivity for the base material on the side opposite to the display surface. It can be used as a transmissive optical element if all of the base material has optical transparency, and as a reflective optical element if the base material opposite to the display surface has optical reflectivity. Can be used. It is also preferable to provide a heat ray reflection layer, an infrared absorption layer, a hard coat layer for increasing the strength, etc. on the substrate. The base material may also serve as the ultraviolet ray shielding layer as described above, and it is preferable to use glass or a polymer resin (film) in which the ultraviolet ray shielding agent is coated or mixed internally as the base material as it is.

Since the optical element of the present invention is particularly suitable as a light control element and a display element for outdoor use, as shown in FIG. 7, a pair of base materials 4 are sealed with a sealing material 5. Is particularly preferable. As such a sealing material (sealing material) 5, any material can be selected as long as it satisfies the following required characteristics, and it is also preferable to use two or more kinds in combination. The properties required of the encapsulant 5 are (1) good adhesion to the base material that constitutes the optical element and the ultraviolet shielding layer, (2) high gas retention, and polymer through the encapsulant. Infiltration of gas into the gel composition and rapid release of the vapor of liquid that causes rapid release of the stimuli-responsive polymer gel inside the optical element, and (3) its characteristics at the contact portion with the polymer gel composition Does not cause a reaction that affects the above, does not release a substance, and (4) has durability such as light resistance and heat resistance depending on the place of use. An adhesive isobutylene-based resin encapsulant or the like can be given as an example of the encapsulating material satisfying such characteristics. Further, as shown in FIG. 8, it is also possible to adopt a configuration in which the sealing materials 5a and 5b are arranged inside and outside and sealing is performed in two stages. In the case of such a two-stage sealing, as the sealing material 5a, a material having a high gas retention property such as a thermoplastic butyl rubber-based sealing material, a polyisobutylene-based sealing material, an adhesive isobutylene-based sealing material, or the like is used. As the encapsulating material 5b, it is preferable to select a material having good adhesiveness such as a deacetic acid type or deoxime type silicone sealing material, an ultraviolet curable acrylic adhesive, or an adhesive isobutylene resin encapsulant. . It should be noted that these encapsulating materials may serve as an ultraviolet blocking layer.

In the optical element of the present invention, when a material having elasticity or fluidity such as polymer gel or polymer liquid is used as the binder (holding member) in the polymer gel composition of the present invention, As shown in FIG. 9, it is also preferable to install a spacer 6 for the purpose of adjusting and maintaining the layer thickness uniformly. Further, the spacer 6 may be installed at the portion where the sealing material 5 is provided. By the action of the spacer 6, even when the polymer gel composition exhibits elasticity or fluidity, the layer thickness of the optical element of the present invention is adjusted and maintained at a desired value, and when used on a vertical surface, Suppression of the deflection of the base material 4 due to the weight of the polymer gel composition and the phenomenon that the layer thickness of the polymer gel composition is different between the upper part and the lower part in the case where a plurality of polymer gel compositions are laminated on the optical element. It is possible to maintain a uniform layer thickness over a long period of time. The spacer 6 may be made of resin, glass, ceramic, or the like, which reacts with the constituent components of the polymer gel composition, or changes its composition due to adsorption or absorption to affect the characteristics. If not, it can be used. Further, regarding the shape, in addition to the rod shape as shown in FIG. 9, various shapes such as a spherical shape, a linear shape, a mesh shape, and a lattice shape can be selected. In the present invention, it is necessary to consider so that this spacer 6 does not become a noticeable visual defect. From these points, it is generally preferable that the material is colorless and transparent glass and the shape is bead-shaped. Becomes When arranging beads, it is preferable to disperse the minimum necessary amount in the polymer gel composition as evenly as possible, and it also depends on the size of the optical element and the layer thickness of the functional material. However, it is about 50 mm x 50 mm
It is a quantitative standard that one or more of them exist in a certain area. If the spacer amount is less than this, spacer 6
There is a possibility that problems may occur as an optical element, such as a corrugated layer thickness of the polymer gel composition in the existing portion and the non-existing portion, and distortion of a transmitted light beam. Further, the spacer 6 may be adhesively fixed if necessary.

In the optical element of the present invention, the preferable range of the thickness of the polymer gel composition or the layer (film-like or plate-like) made of the same is not particularly limited, but preferably in the range of 1 μm to 3 mm. More preferably 20 to 1
The range is 000 μm. If the thickness is less than 1 μm, the mechanical strength may be weakened, and the desired optical density may not be obtained due to the short optical path length.
If it is thicker than that, the polymer gel composition may have poor responsiveness, and the stimuli-responsive polymer gel may be stacked more than necessary, resulting in problems such as insufficient transmittance.

The operation of the polymer gel composition (optical element) of the present invention will now be described. As illustrated in FIG. 10, in the polymer gel composition, the stimuli-responsive polymer gel 1 causes a volume change due to swelling (a) and contraction (b) due to stimulation, and scatters or diffracts light transmittance and the like. Can be changed by Here, FIG. 10 is a schematic cross-sectional view for explaining the operation of the polymer gel composition of the present invention, where (a) represents the swelling of one stimuli-responsive polymer gel particle, and (b) represents The time when one particle of the stimuli-responsive polymer gel contracts is shown. Further, when the stimuli-responsive polymer gel 1 contains a dimming material having a saturated absorption concentration or a saturated absorption / scattering concentration or more, the light absorption or scattering efficiency depends on the volume change of the stimulus-responsive polymer gel 1. Can be changed to change the optical density. Specifically, the optical density becomes high when the stimuli-responsive polymer gel 1 swells, and becomes low when it contracts.
Therefore, the polymer gel composition of the present invention can be suitably used as an optical element such as a light control element or a display element.

Although the preferred embodiments of the present invention have been described above, the present invention can be variously modified and changed within the scope of the gist thereof.

[0085]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, each of these examples does not limit the present invention.

(Preparation of Polymer Gel Particles) -Preparation of Stimulus-Responsive Polymer Gel Particles A-Stimulus-responsive polymer gel A particles were prepared by the following process. N-isopropylacrylamide (3.5758g), methylenebisacrylamide (0.0072g), microencapsulated carbon black dispersion (Dainippon Ink and Chemicals, MC black
082-E, containing 14.3% of pigment content) of water (19.16)
Dissolved oxygen was removed by passing nitrogen through the solution for 30 minutes.
APS (29.9 mg) of water (0.5
106 g) solution was added and stirred to dissolve uniformly. 75
A cyclohexane (1.2 L) solution of Sorgen 50 (6.00 g) was placed in a 2 L separable flask equipped with a 3-blade stirring blade with a diameter of mm, and the NI was adjusted earlier.
The PAM pigment dispersion was added, and nitrogen was flushed to replace the entire inside of the flask with nitrogen. Keep the entire flask at 25 ° C using a water bath, and stir the blade at 800 rpm for 15 minutes.
The aqueous phase was suspended and dispersed in cyclohexane by rotating for a minute. The rotation speed of the stirring blade was set to 250 rpm, a cyclohexane (3.2 ml) solution of TMEDA (0.8 ml) was added to this dispersion liquid to start the reaction, and the temperature was adjusted to 25 ° C.
Polymerization was carried out at 250 rpm for 2 hours while maintaining The obtained polymer particles were thoroughly washed with dimethylformamide and water. In this way, stimuli-responsive polymer gel particles A were produced. The synthesized stimuli-responsive polymer gel particles had a volume average particle diameter of 30 μm at room temperature (25 ° C., swollen state). The stimuli-responsive polymer gel particles had a phase transition temperature at about 34 ° C. That is, the polymer gel particles contract at a temperature higher than the phase transition point and swell at a low temperature. The volume change was about 15 times.

—Preparation of Stimulus-Responsive Polymer Gel Particle B— Stimulus-Responsive (High Temperature Swelling) Polymer Gel B Containing Coloring Material
Particles were produced by the following process. 1.0 g of acrylamide, 1.0 mg of methylenebisacrylamide as a cross-linking agent, 0.575 g of distilled water, a black pigment as a coloring material (manufactured by Dainippon Ink and Chemicals, MCblack
082-E, containing 14.3% of pigment content) 3.4
An aqueous solution B was prepared by mixing 25 g with stirring. Sorbitol surfactant (Solgen 50: Daiichi Kogyo Seiyaku Co., Ltd.)
A solution prepared by dissolving 2.375 g of toluene in 300 ml of toluene was added to a reaction vessel in which the atmosphere was replaced with nitrogen, and the aqueous solution B prepared above was added to the solution.
Stirring was carried out at rpm for 30 minutes to obtain a suspension B. The resulting suspension B was placed in a flask, oxygen was removed by nitrogen substitution, and then a solution prepared by dissolving 0.004 g of ammonium persulfate as a polymerization initiator in 0.5 ml of water was added,
Polymerization was carried out by heating at 70 ° C for 3 hours. After completion of polymerization
Purification was performed by washing with a large amount of acetone, and further drying was performed to obtain acrylamide gel particles containing a coloring material. Next, 1.5 g of acrylic acid, 0.0015 g of methylenebisacrylamide as a cross-linking agent, and 5.5 g of distilled water were mixed, and after nitrogen substitution, 0.006 g of ammonium persulfate was dissolved in 0.5 g of water. Was added to obtain a mixed solution. 0.5 g of the acrylamide gel particles obtained above was added to this mixed solution and heated to 70 ° C.
Polymerization was carried out for a period of time to prepare IPN polymer gel particles B (stimulus-responsive polymer gel particles B).

The thus obtained IPN polymer gel particles (acrylic acid-acrylamide interpenetrating network structure gel particles) were put into a large amount of distilled water, and heated and cooled to swell and shrink the gel particles, followed by filtration. The purification was repeated. The volume average particle diameter of the obtained IPN polymer gel particles when dried was about 15 μm. The IPN polymer gel particles were added to a large amount of pure water and swollen. This IP
The water absorption amount of the N polymer gel particles at equilibrium swelling at 10 ° C. was about 3 g / g. However, it was found that when it was heated to 50 ° C., it swelled further and exhibited a water absorption of about 80 g / g. This phase transition point was in the temperature range of 30-40 ° C. That is, it swells at a temperature higher than the phase transition point and contracts at a low temperature. This change is reversible, and the particle size of the polymer gel particles during swelling changes up to about 3 times that during contraction,
That is, a change of about 27 times in volume was obtained.

(Preparation of Dispersion Liquid) -Preparation of Dispersion Liquid A-An aqueous dispersion solution (concentration of gel solid content: 2.5%) containing stimuli-responsive polymer gel particles A at a constant concentration was prepared. 10 g of this water dispersion fluorine-based ultraviolet curable resin (K manufactured by Nippon Kayaku Co., Ltd.
AYARAD FAD-515) Fluorosurfactant (Surflon S-383 manufactured by Seimi Chemical Co., Ltd.) 5
It was added to 10 g of a mass% solution and cooled to 0 ° C. This liquid was dispersed with a wave rotor to disperse an aqueous dispersion of stimulus-responsive polymer gel particles A in an ultraviolet curable resin to prepare dispersion A.

-Preparation of Dispersion B- With the same composition as Dispersion A, Vio as an ultraviolet absorber
Dispersion B was prepared by adding 0.5 g of sorb 105 (manufactured by Kyodo Chemical Co., Ltd.).

—Preparation of Dispersion C— An aqueous dispersion (concentration of gel solid content: 2.5%) containing a constant concentration of stimuli-responsive polymer gel particles B was prepared. 10 g of this water dispersion fluorine-based ultraviolet curable resin (K manufactured by Nippon Kayaku Co., Ltd.
AYARAD FAD-515) Fluorosurfactant (Surflon S-383 manufactured by Seimi Chemical Co., Ltd.) 5
It was added to 10 g of a mass% solution and cooled to 0 ° C. This liquid was dispersed with a wave rotor to disperse an aqueous dispersion of stimuli-responsive polymer gel particles B in an ultraviolet curable resin to prepare dispersion C).

-Preparation of Dispersion D- An aqueous dispersion solution (concentration of gel solid content: 2.5%) containing a constant concentration of stimuli-responsive polymer gel particles A was prepared. To 10 ml of this aqueous solution, polyvinyl alcohol (manufactured by Shin-Etsu Chemical)
A 7.5 mass% aqueous solution of Poval C-25GP) was added to 10
0.12 ml of sodium dodecyl sulfate as an additive
g was added and stirred to uniformly disperse the polymer gel particles to prepare Dispersion D.

Examples 1 to 8 and Comparative Examples 1 and 2 (Preparation of polymer gel composition) According to Table 1, optical elements were prepared as follows. Dispersions A to C are each formed on a glass substrate with a blade coater to a thickness of 150 mm.
A film-shaped molded product (polymer gel composition) was formed on.
UV irradiation (high pressure mercury lamp, 160W / cm, irradiation distance 2
(0 cm, 10 seconds irradiation) to cure. Furthermore, 2
The film-shaped molded product was sandwiched between a plurality of substrates (substrate X, substrate Y, 50 × 50 mm). At this time, an ultraviolet protection layer was provided if necessary. At this time, when providing an ultraviolet protection layer,
It was provided between the substrate Y and the film-shaped molded product. Further, the periphery was sealed with a thermoplastic butyl rubber and a photosensitive acrylic adhesive (KAYARAD R381I manufactured by Nippon Kayaku). In this way, an optical element was produced.

[0094]

[Table 1]

(Example 9) Dispersion D (polymer gel composition) was used between two substrates (white glass, UV cut glass (Niseki Mitsubishi Corp.) using polystyrene beads having a particle size of 100 μm as a spacer. NOUVIO410), 50
X 50 mm). Furthermore, the surrounding area is thermoplastic butyl rubber and a photosensitive acrylic adhesive (Nippon Kayaku
The periphery was sealed with KAYARAD R381I). In this way, an optical element was produced.

(Evaluation of Function) Each of the manufactured optical elements was equipped with a weather meter (Suntest CPS manufactured by Toyo Seiki Co., Ltd.).
Accelerated tests were carried out by exposure in +) for 1500 hours. The results are the appearance of the internal gel particles by microscopic observation after the acceleration test, the volume ratio between swelling and contraction when responding to a stimulus, and visible light (400-800) during coloring and erasing.
(average of nm) transmitted light amount difference ((visible light transmittance during contraction)-(visible light transmittance during swelling), reflected light amount difference when white glass is used) and JIS Z 8730. It was evaluated by the color difference at the time of erasing. The results are shown in Table 2. The visible light transmittance was evaluated by the change in the amount of transmitted light of the polymer gel composition (light control layer), using the same substrate as in the examples and comparative examples without reference to the polymer gel composition.

[0097]

[Table 2]

From these examples, a polymer containing a swelling liquid, a polymer gel that causes a reversible volume change by absorbing or releasing the swelling liquid in response to a stimulus, and a binder that covers at least the polymer gel Gel composition (optical element)
It can be seen that is extremely widened in light resistance (especially ultraviolet light) by an ultraviolet light shielding means such as addition of an ultraviolet light shielding agent to the binder or provision of an ultraviolet light shielding layer.

[0099]

As described above, according to the present invention, a large area can be easily obtained at low cost, a large change in light transmittance (high contrast ratio), and long-term light (especially ultraviolet ray) durability. A polymer gel composition and an optical element using the same can be provided.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a polymer gel composition (optical element) of the present invention.

FIG. 2 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 3 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 5 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 6 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 7 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 8 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 9 is a schematic cross-sectional view showing another example of the polymer gel composition (optical element) of the present invention.

FIG. 10 is a schematic cross-sectional view for explaining the operation of the polymer gel composition (optical element) of the present invention, where (a) represents the swelling of stimuli-responsive polymer gel particles and (b) represents (b). The time of contraction of the stimuli-responsive polymer gel particles is shown.

[Explanation of symbols]

1 Stimuli-responsive polymer gel 2 Holding member (binder) 3 UV shielding layer 4 base material 5, 5a, 5b Sealing material 6 spacers

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G02F 1/17 G02F 1/17 1/19 1/19 (72) Inventor Shoichiro Fujiwara Takematsu, Minamiashigara City, Kanagawa Prefecture 1600 Fuji Xerox Co., Ltd. (72) Inventor Kazushiro Akashi 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. F term (reference) 4J002 BB031 BB121 BB171 BC031 BC061 BD041 BD101 BD121 BD141 BE021 BE061 BG001 BG012 BG132 BH022 BN071 BN121 BN151 BQ002 CB001 CF061 CF071 CF161 CG001 CH071 CK021 CL001 CN011 CN031 DE096 DE106 DE136 DE236 DJ036 DJ046 DJ056 EE036 ET006 EU176 FD056 GT00

Claims (16)

[Claims] 1. A swelling liquid, a stimuli-responsive polymer gel that causes a volume change by absorbing and releasing the swelling liquid in response to a stimulus, and a binder that covers at least the stimulus-responsive polymer gel. What is claimed is: 1. A polymer gel composition, which comprises an ultraviolet light shielding means for shielding the ultraviolet light incident on the polymer gel composition. 2. The polymer gel composition according to claim 1, wherein an ultraviolet blocking agent is contained in the binder as the ultraviolet blocking means. 3. The polymer gel composition according to claim 2, wherein the ultraviolet blocking agent is selected from a benzophenone compound, a benzotriazole compound, and a cyanoacrylate compound. 4. The ultraviolet light shielding means according to claim 1, wherein an ultraviolet light shielding layer is provided on at least a part of the outer surface of the polymer gel composition as the ultraviolet light shielding means. Molecular gel composition. 5. The polymer gel composition according to claim 4, wherein the ultraviolet shielding layer is a polymer resin layer having an ultraviolet shielding function. 6. The polymer gel composition according to claim 4, wherein the ultraviolet shielding layer is a glass layer having an ultraviolet shielding function. 7. The polymer gel composition according to claim 1, wherein the stimuli-responsive polymer gel contains a light control material. 8. The light control material is a coloring material and / or a light scattering material, and is contained in the stimuli-responsive polymer gel at a saturated absorption concentration or higher or a saturated scattering concentration or higher. The polymer gel composition according to claim 7. 9. The polymer gel composition according to claim 1, wherein the binder is made of resin. 10. An optical element comprising the polymer gel composition according to claim 1. 11. The optical element according to claim 10, wherein the polymer gel composition is sandwiched between a pair of base materials. 12. The optical element according to claim 11, wherein a space between the pair of base materials is sealed. 13. At least one of the pair of base materials comprises:
It has optical transparency, It is characterized by the above-mentioned.
The optical element according to 1. 14. At least one of the pair of base materials comprises:
2. A polymer resin film as claimed in claim 1.
The optical element according to any one of 1 to 13. 15. At least one of the pair of base materials comprises:
It consists of glass, The optical element in any one of Claims 11-13 characterized by the above-mentioned. 16. At least one of the pair of base materials comprises:
The optical element according to claim 11, which has light reflectivity.