JP2013190547A - Gel-like polymer device exhibiting electrooptic effect and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gel-like polymer device exhibiting an electrooptic effect which has small energy loss and can be applied for new applications and a method for manufacturing the same.SOLUTION: The gel-like polymer device comprises: a high-dielectric gel-like polymer material 2 exhibiting an electrooptic effect; and an electrode 3 for applying a bias voltage to the gel-like polymer material 2, in which the gel-like polymer material 2 has a relative permittivity of 1×10or more at 0.01 Hz. Examples of an insulating polymer compound constituting the gel-like polymer material 2 include one or more polymer compounds selected from the group consisting of polyvinyl chloride, polyacrylonitrile, nylon, polyethylene terephthalate, polypropylene, polyethylene, polyketone, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, poly(n-butyl acrylate), cellulose and wool. The gel-like polymer material preferably has a relative permittivity of 10or more at 0.001 Hz.

Description

  The present invention relates to a gel polymer device (polymer element) exhibiting an electro-optic effect and a manufacturing method thereof, and more specifically, an electric field control type thin film Fresnel lens, an electric field control type optical waveguide switch, and a refractive index by an electric field without deformation. The present invention relates to a gel polymer device that can be used for a control element, an electric field sensitive photoresponsive sensor, and the like, and a manufacturing method thereof.

  Polyvinyl chloride (PVC) is widely used as a low dielectric insulating polymer resin. PVC plasticized flexible bodies (hereinafter referred to as “plasticized PVC”), which is a flexible polymer material in which a plasticizer is added to PVC, are also used in various fields such as tapes, tubes, and wallpaper. ing. Plasticizers are also low dielectric constant chemicals. Both PVC resin and plasticized PVC have excellent performance as a low dielectric constant material, and many applications have been developed. These materials are materials that are expected to have a stable insulation property against electric field application. On the other hand, these materials are not expected to respond autonomously to stimuli such as an external electric field.

  As a material that autonomously drives in response to an electric field, a material that is obvious to respond to an electric field, such as an ion conductive polymer (polymer electrolyte), is generally known. However, although the driving element using the ion conductive polymer is driven by a low electric field, the deformation mode (mainly bending deformation) is limited and the energy loss due to the current is large, so that sufficient performance (stress, Speed etc.) is difficult to obtain.

  Conductive polymers are also used as materials for drive elements. This conductive polymer is also known to respond to an electric field, and a driving element utilizing asymmetric medium adsorption has been developed and attracting attention. However, as in the case of the ion conductive polymer, energy loss such as heat generation due to current cannot be avoided, and it cannot be a practical driving element in terms of durability.

  The present inventor has found that plasticizing PVC having a low dielectric constant causes extremely specific large deformation by applying an electric field, contrary to common sense, and is considering application to a driving element (Patent Document 1 and Non-Patent Document 1). (See Patent Document 1).

JP 2010-191048 A

US Patent 7,933,081

  An object of the present invention is to provide a gel-like polymer device having a small energy loss and exhibiting an electro-optic effect that can be applied to new applications, and a method for producing the same.

  PVC, which is a low dielectric general-purpose polymer material, has not been noticed because it cannot be expected to be responsive to an electric field. However, as described above, the present inventors have applied an electric field to plasticized PVC having a low dielectric constant. It was found that a very specific large deformation was caused by applying. Furthermore, the present inventor has focused on elucidating the actual state that plasticized PVC must have electrorheologically specific characteristics as a principle of deformation of plasticized PVC.

  The present inventor has found that the dielectric constant of a specific plasticized PVC significantly increases in the DC electric field region in the process of elucidating the principle of a gel-like polymer material such as plasticized PVC. The dielectric constant value was similar to that of potassium niobate tantalate niobate, which is a ferroelectric material and exhibits an electro-optic effect. Therefore, it is expected that plasticized PVC will also exhibit the same electro-optic effect, and further research The present invention was completed by repeating the above.

That is, a gel polymer device according to the present invention for solving the above-described problems has a high dielectric gel polymer material exhibiting an electro-optic effect and an electrode for applying a bias voltage to the gel polymer material. The gel-like polymer material has a relative dielectric constant of 1 × 10 ⁴ or more at 0.01 Hz.

  According to this invention, since it has a high dielectric gel-like polymer material exhibiting an electro-optic effect and an electrode to which a bias voltage is applied, the gel-like polymer material is an ion conductive polymer material or a conductive polymer. Even if it is not a material, the superparaelectric properties induced by the applied bias voltage provide an electro-optic effect. As a result, the gel polymer device exhibiting the electro-optic effect can be applied to an optical driving element or a refractive index control material by an electric field. And such a gel-like polymer device has a small energy loss, and can be utilized as a functional element expected for a new application.

In the gel polymer device according to the present invention, the dielectric constant of the gel polymer material is preferably 1 × 10 ⁵ or more at 0.001 Hz.

  In the gel polymer device according to the present invention, the insulating polymer compound constituting the gel polymer material is polyvinyl chloride (PVC), polyacrylonitrile (PAN), nylon (Nylon), polyethylene terephthalate (PET), From the group of polypropylene (PP), polyethylene (PE), polyketone (PK), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), poly nbutyl acrylate (PnBA), cellulose, wool, etc. Any one or two or more polymer compounds selected.

  The method for producing a gel polymer device according to the present invention for solving the above-described problem is a method for producing the gel polymer device according to the present invention, wherein an electro-optic effect is obtained by forming an insulating polymer compound in a gel form. And a step of preparing an electrode for applying a bias voltage to the gel-like polymer material.

  According to the gel polymer device and the manufacturing method thereof according to the present invention, the bias applied even if the gel polymer material constituting the gel polymer device is not an ion conductive polymer material or a conductive polymer material. Superparaelectric properties induced by voltage provide an electro-optic effect. As a result, the gel polymer device exhibiting the electro-optic effect can be applied to an optical driving element or a refractive index control material by an electric field. And such a gel-like polymer device has a small energy loss, and can be utilized as a functional element expected for a new application.

It is a typical block diagram which shows an example of the gel-like polymer device which concerns on this invention. It is a graph which shows the time-dependent change of the laser spot position at the time of the x-axis direction at the time of applying an electric field to the gel-like polymer device produced by making mass ratio of PVC: DBA 1: 5. It is a graph which shows the electric field dependence of the refraction angle of the laser to a x-axis direction. It is a typical block diagram which shows another example of a gel-like polymer device. It is a schematic diagram which shows the focus change of the lens in each ON / OFF of an electric field. It is the plane | planar photograph (a) (b) and front photograph (c) (b) of a lens in each ON / OFF of an electric field.

  Hereinafter, although the gel-like polymer device concerning the present invention and its manufacturing method are explained, the present invention is not limited only to the contents indicated in the following explanation and drawings.

As shown in FIG. 1, a gel polymer device 1 according to the present invention includes a high dielectric gel polymer material 2 exhibiting an electro-optic effect, and an electrode for applying a bias voltage to the gel polymer material 2. 3 and 3, and the specific dielectric constant of the gel polymer material 2 is 1 × 10 ⁴ or more at 0.01 Hz. The “electro-optic effect” is a phenomenon in which the optical properties such as the refractive index and absorbance of the substance change depending on the electric field. In particular, the phenomenon in which the refractive index of the substance changes in proportion to the square of the electric field is called the Kerr effect. However, the present invention provides such an electro-optic effect and similar effects, and specifically finds an effect that changes occur in the optical element due to a very specific large deformation when an electric field is applied. It was.

  Hereinafter, each component will be described.

(Gel polymer material)
The gel-like polymer material 2 is a gel having a high dielectric property (Corrosal dielectric property) in a DC electric field region. The DC electric field region is a frequency region in the range of about 0.001 Hz to 0.01 Hz, and its high dielectric property has a relative dielectric constant of 1 × 10 ⁴ or more at 0.01 Hz. Further, it preferably has a relative dielectric constant of 1 × 10 ⁵ or more at 0.001 Hz.

The gel-like polymer material 2 does not include an ionic material or a conductive material, and does not exhibit ionic conductivity or electrical conductivity based on the ionic material or conductive material. Nevertheless, when a bias voltage in the DC electric field region is applied, a high dielectric constant that cannot be imagined from the dielectric constant of the insulating polymer compound mainly constituting the gel polymer material 2 is exhibited. The dielectric constant depends on the type of gel-like polymer material 2 and the degree of gelation, and thus cannot be generally stated. For example, as shown in Example 1 described later, a gel-like dielectric having a relative dielectric constant of about 10 When a bias voltage of 0.001 Hz is applied to the polymer material 2, the relative dielectric constant of the gel polymer material 2 can be increased to 1 × 10 ⁵ or more, and in the case of remarkable, about 1 × 10 ⁶ . Further, even when a bias voltage of 100 Hz, which is a low frequency, is applied, a high relative dielectric constant of 100 or more is exhibited.

  Such high dielectric properties (superparaelectricity) are known for inorganic materials such as potassium niobate tantalate, but are not known for general-purpose polymers that are low dielectric constant materials. It can be said that it is superparaelectric. Gel polymer material 2 exhibits superparaelectricity, but on the other hand, it is a high-resistance material, so energy loss due to current leakage (0.1 μA) is negligible compared to conventional polymer electrolyte systems (several mA). As small as possible. Therefore, there is an advantage that it can be applied to a super energy saving and ultra high efficiency device.

(Insulating polymer compound)
The gel-like polymer material 2 mainly contains an insulating polymer compound. That is, the insulating polymer compound is a compound constituting the gel polymer material 2 and does not include an ionic material or a conductive material, and is an insulating material that does not exhibit ionic conductivity or electrical conductivity. . Before this insulating polymer compound is mixed with a gelling agent such as a plasticizer or an organic solvent described later to form a gel, it is a general insulating polymer compound. Such an insulating polymer compound has a low dielectric constant, and usually has a relative dielectric constant of about 2 to 9. However, since the gel polymer material 2 obtained by gelling the insulating polymer compound does not include an ionic material or a conductive material, energy loss such as heat generation due to a current flowing based on the ionic material or the conductive material. Is extremely small.

  Examples of the insulating polymer compound include polyvinyl chloride (PVC), polyacrylonitrile (PAN), nylon (Nylon), polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polyketone (PK), polyvinyl It is possible to use any one or two or more polymer compounds selected from the group consisting of alcohol (PVA), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), poly nbutyl acrylate (PnBA), cellulose, wool and the like. it can.

(Gelation)
The gel polymer material 2 is obtained by gelling the insulating polymer compound. Gelation can be performed by adding a gelling agent to the insulating polymer compound. For example, a plasticizer or an organic solvent can be used as the gelling agent, although it depends on the type of the insulating polymer compound. The amount of the gelling agent such as a plasticizer or an organic solvent is determined so as to obtain a desired gel strength.

The gel strength is preferably in a range of 2 kg / cm ² or more 5 kg / cm ² or less, the gel strength by this range can be applied to various applications as gel polymer device 1. When the gel strength is less than 2 kg / cm ^{2, the} gel strength is too soft to be measured, and in some cases, the gel strength may not be used as the gel polymer device 1. On the other hand, when the gel strength exceeds 5 kg / cm ² , the gel strength becomes hard and may not be used as the gel polymer device 1. The gel strength can be measured by forming the gel polymer material 2 into a sample shape for measurement using a tensile tester.

  As a plasticizer blended for gelation, a known insulating plasticizer can be used. For example, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dibutyl phthalate (di-n-butyl phthalate); adipic acid esters such as dioctyl adipate, diisononyl adipate; trioctyl trimellitic acid, etc. Polyester; Phosphate ester such as tricresyl phosphate; Citric acid ester such as acetyltributyl citrate; Epoxidized vegetable oil such as epoxidized soybean oil and epoxidized linseed oil; Sebacic acid ester; Azelaic acid ester; Maleic acid ester; benzoic acid ester and the like.

  Which plasticizer is used is selected depending on the type of the insulating polymer compound. Further, the blending ratio of the plasticizer is set depending on the type of the insulating polymer compound, but it is usually preferable to blend a large amount of the plasticizer. The blending ratio is preferably in the range of insulating polymer compound: plasticizer (mass ratio) = 1: 2 to 1:20. Thus, by increasing the blending amount of the plasticizer to several to 20 times the blending amount of a general plasticizer and increasing the blending ratio of the plasticizer, the situation is completely changed from the conventional one, and superparaelectricity The gel-like polymer material 2 having an electro-optic effect can be obtained.

  As an organic solvent blended for gelation, an organic solvent having a low dielectric constant (ε = 2 to 8) such as benzene or toluene may be used, or a high solvent such as dimethyl sulfoxide (DMSO) or dimethylformamide (DMF). An organic solvent having a dielectric constant (ε = 20 to 40) may be used.

  Which organic solvent is used is selected depending on the type of the insulating polymer compound. Further, the blending ratio of the organic solvent is also set depending on the type of the insulating polymer compound, but usually the organic solvent is not blended as much as the plasticizer described above. The blending ratio is preferably in the range of insulating polymer compound: organic solvent (mass ratio) = 1: 2 to 1: 8. Thus, by making the blending amount of the organic solvent larger than the blending amount of the general organic solvent, the situation is completely changed from that of the conventional one, and the gel-like polymer material 2 having a colossal dielectric property can be obtained. it can.

  If the blending ratio of the plasticizer and organic solvent is increased, the mechanical properties decrease, and the gel form changes to the sol form, so that it cannot be used. However, even if a large amount of plasticizer or organic solvent is blended, By adjusting the molecular weight or the like of the insulating polymer compound so that the gel state can be maintained, the gel polymer material 2 having a huge dielectric constant can be obtained. Specifically, an insulating polymer compound whose molecular weight (weight average molecular weight) is adjusted so as to be in the above-described gel strength range is used.

The molecular weight of such an insulating polymer compound can be, for example, 1 × 10 ⁴ or more and 1 × 10 ⁶ or less, and the molecular weight can be adjusted and used within this range. For example, it is preferable to use an insulating polymer compound having a large molecular weight when it is too soft, and to use an insulating polymer compound having a small molecular weight when it is too hard.

(electrode)
The electrode 3 is provided for applying a DC voltage or a low-frequency bias voltage (0.001 Hz, 0.01 Hz, etc.) to the gel polymer material 2. Although arrangement | positioning of the electrode 3 is not specifically limited, For example, as shown in FIG. 1, it is provided so that the gel-like polymer material 2 may be pinched | interposed. The material constituting the electrode 3 is not particularly limited, and a known electrode material such as a metal material such as aluminum, copper or titanium, a conductive inorganic material such as indium tin oxide or carbon material, or a conductive organic material is selected and used. be able to. The shape of the electrode is not particularly limited, and may be any shape according to the shape of the gel-like polymer device 1 such as a sheet shape or a film shape.

  The electrode 3 is connected to a power source, and a DC voltage or a low-frequency bias voltage is supplied from the power source.

  As described above, according to the gel polymer device 1 and the manufacturing method thereof according to the present invention, the gel polymer material 2 constituting the gel polymer device 1 is an ion conductive polymer material or a conductive polymer material. If not, the superparaelectric properties induced by the applied bias voltage provide an electro-optic effect. As a result, the gel polymer device 1 showing the electro-optic effect can be applied to an optical driving element or a refractive index control material by an electric field. And such a gel-like polymer device 1 has a small energy loss, and can be utilized as a functional element expected for new applications.

  In particular, an electric field control type thin film Fresnel lens, an electric field control type optical waveguide switch, a refractive index control element using an electric field without deformation, an electric field sensitive photoresponse sensor, and the like can be given.

  The present invention will be specifically described by the following experimental examples.

[Experiment 1]
Polyvinyl chloride (PVC) having a polymerization degree of 1140 and dibutyl adipate (DBA) were blended at a mass ratio of 1: 2, 1: 5, 1: 8, and sufficiently stirred. Each solution was poured into a glass cell preheated at 150 ° C. An aluminum electrode was previously placed on the opposing wall surface of the glass cell, and the injected solution was heated at 150 ° C. for 20 to 30 minutes to produce a gel-like plasticized PVC between the electrodes. Thus, three types of gel polymer devices 1 were obtained.

(Measurement)
The produced gel-like polymer device 1 was irradiated with a He—Ne laser (wavelength 633 nm, output 5 mW), and an electric field was applied at a constant period to be 250 V / mm. The transmitted laser was projected onto the screen, and the movement of the laser spot was photographed with a video camera. The time-dependent change of the laser spot position was graphed by moving image analysis and shown in FIG. Further, regarding the gel polymer device 1 having a mass ratio of 1: 5, the displacement amount of the laser spot when an electric field was applied was determined, and the refraction angle of the laser was calculated. Moreover, the dielectric constant of the gel-like polymer device 1 was measured at all measurement frequencies using an impedance measuring apparatus.

(result)
FIG. 2 shows the change with time in the x-axis direction of the laser spot position when an electric field is applied to the gel polymer device 1 manufactured with a PVC: DBA mass ratio of 1: 5. In FIG. 2, the spot position before applying an electric field is set to 0, and the spot position for every minute is plotted. From the result of FIG. 2, it can be seen that the spot position changes according to the ON / OFF of the electric field. Further, the displacement amount showed a large value of about ± 15 mm in the first cycle, but a substantially constant value of about ± 5 mm to ± 7 mm after the second cycle.

The amount of displacement of the laser spot position was examined for the gel polymer device 1 with each mass ratio. As a result, the magnitude of the displacement amount was 1: 5> 1: 8> 1: 2. The dielectric constant of the gel-like polymer device 1 used in the experiment is 0.01 Hz which is a DC electric field region, and the gel-like polymer device 1 having a mass ratio of 1: 5 is the highest at 1 × 10 ⁵ or more and close to 1 × 10 ^6. The gel polymer device 1 having a mass ratio of 1: 8 was 1 × 10 ⁴ , and the gel polymer device 1 having a mass ratio of 1: 2 was 1 × 10 ³ . From this result, a preferable mass ratio can be set to 1: 5 to 1: 8. Further, at a mass ratio of 1: 5 to 1: 8, it exceeded 100 even with a bias voltage of 100 Hz. It was found that the displacement amount of the spot position and the dielectric constant of the gel-like polymer device 1 coincided, and the displacement amount of the laser spot position is proportional to the dielectric constant of the gel-like polymer device 1.

  FIG. 3 is a graph showing the electric field dependence of the laser refraction angle in the x-axis direction. In the case of the Kerr effect, since the refractive index of the laser is proportional to the square of the electric field, it was confirmed that the gel polymer device 1 also exhibits the Kerr effect. Specific refraction angles were 0.5 ° at 250 V / mm, 0.3 ° at 200 V / mm, 0.15 ° at 150 V / mm, and 0.05 ° at 100 V / mm. A desired refraction angle can be obtained by changing the voltage.

  As described above, from the relationship between the displacement of the spot position of the laser beam that has passed through the gel polymer device 1 under the application of a DC electric field and the dielectric constant, and the relationship between the refraction angle of the laser and the electric field strength, the gel polymer device. The car effect of 1 was confirmed.

[Experiment 2]
As an application experiment of the gel polymer device 1, an electric field control type thin film lens was produced using the gel polymer material 2 of Example 1 (PVC: DBA = 1: 5). FIG. 4 is a configuration diagram thereof, in which a cathode electrode 3 (glass with ITO) is provided under the lens-like gel-like polymer material 2 so that the lens-like gel-like polymer material 2 is sandwiched in plan view. An anode electrode 3 (glass with ITO) was provided. A DC voltage was applied between the cathode electrode 3 and the anode electrode 3, and an insulating film was provided at a location where both electrodes overlapped so that the cathode electrode 3 and the anode electrode 3 did not contact each other. FIG. 5 is a schematic diagram showing a change in focus of the lens when the voltage is applied to the lens-like gel-like polymer material 2, and FIG. 6 is an actual plan photograph (a) (b) at that time. ) And front photographs (c) and (b).

  As can be seen from the results of FIG. 6, by applying a DC voltage to the lens-like gel-like polymer material 2, the gel-like polymer material 2 was greatly deformed and caused a focus change as shown in FIG. . As described above, in the present invention, an optical element such as a focal point can be changed by applying an electric field to cause a large deformation in the gel polymer device 1.

1 Gel Polymer Device 2 Gel Polymer Material 3 Electrode

Claims (4)

A high dielectric gel-like polymer material exhibiting an electro-optic effect; and an electrode for applying a bias voltage to the gel-like polymer material, wherein the dielectric constant of the gel-like polymer material is 1 × at 0.01 Hz. A gel polymer device, characterized in that it is 10 ⁴ or more. 2. The gel polymer device according to claim 1, wherein a relative dielectric constant of the gel polymer material is 1 × 10 ⁵ or more at 0.001 Hz.   The insulating polymer compound constituting the gel polymer material is polyvinyl chloride, polyacrylonitrile, nylon, polyethylene terephthalate, polypropylene, polyethylene, polyketone, polyvinyl alcohol, polyvinyl acetate, polymethyl methacrylate, poly nbutyl acrylate, The gel-like polymer device according to claim 1 or 2, which is any one or two or more polymer compounds selected from the group consisting of cellulose and wool.   A step of preparing an insulating polymer compound in a gel state and preparing a highly dielectric gel-like polymer material exhibiting an electro-optic effect; a step of forming an electrode for applying a bias voltage to the gel-like polymer material; A method for producing a gel-like polymer device, comprising: