JP2013192333A - Gelatinous polymer device having colossal dielectricity and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gelatinous polymer device having a colossal dielectricity using a gelatinous polymer material applicable to new applications.SOLUTION: A gelatinous polymer device 1 comprises: a gelatinous polymer material 2 having colossal dielectricity; and electrodes 3, 3 for applying a low frequency bias voltage to the gelatinous polymer material 2. The insulating polymer compound composing the gelatinous polymer material 2 includes any one or more than one polymer compound selected from a group of polyvinyl chloride, polyacrylonitrile, nylon, polyethylene terephthalate, polypropylene, polyethylene, polyketone, polyvinyl alcohol, polyvinyl acetate, polymethyl metacrylate, poly n-butyl acrylate, cellulose, wool, and the like. Relative permittivity of the gelatinous polymer material 2 is 1000 or more at 1 Hz, and 100 or more at 10 Hz.

Description

  The present invention relates to a gel-like polymer device (polymer element) having a colossal dielectric property (also referred to as giant dielectric property) and a manufacturing method thereof, and more specifically, a fine actuator element, an autonomously responsive deformation material, a soft chuck, a fine chuck, The present invention relates to a gel-like polymer device that can be used for a component conveying function material, a micro switch, a micro valve, a micro pump, a Microsoft telescopic actuator, a micro finger, a deformation sensor, a pressure sensor actuator, 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

  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 invention was discovered in the process of elucidating the principle of such a gel-like polymer material such as plasticized PVC, and its purpose is low energy loss and has a corrosal dielectric that can be applied to new applications. The object is to provide a gel polymer device and a method for producing the same.

  In the process of elucidating the principle of a gel-like polymer material such as plasticized PVC, the present inventor has found that a specific plasticized PVC exhibits a very large dielectric constant when an electric field is applied in a low frequency range. The present invention has been completed based on these findings.

  A gel-like polymer device according to the present invention for solving the above-described problems has a gel-like polymer material having a corrosal dielectric property and an electrode for applying a low-frequency bias voltage to the gel-like polymer material. Features.

  According to the present invention, since the gel-like polymer material having the colossal dielectric property and the electrode for applying the low-frequency bias voltage are included, the gel-like polymer material is an ion conductive polymer material or a conductive polymer. Even if it is not a material, it is driven autonomously in response to an applied bias voltage. Such a gel polymer device has a small energy loss and can be used as a functional element expected for new applications.

  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.

  In the gel polymer device according to the present invention, the gel polymer material has a relative dielectric constant of 1000 or more at 1 Hz and 100 or more at 10 Hz.

  The method for producing a gel polymer device according to the present invention for solving the above-mentioned problem is a method for producing the gel polymer device according to the present invention, wherein the insulating polymer compound is made into a gel and is subjected to a collosal dielectric property. And a step of forming an electrode for applying a low-frequency bias voltage to the gel-like polymer material.

  According to the gel polymer device and the manufacturing method thereof according to the present invention, since the gel polymer material having the colossal dielectric property is included, the gel polymer material is an ion conductive polymer material or a conductive polymer material. Even if not, it is driven autonomously in response to the applied bias voltage. Such a gel polymer device has a small energy loss and can be used as a functional element expected for new applications.

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 FT-IR spectrum of PVA (degree of polymerization 1000) / DMSO gel. It is a graph which shows the dielectric constant of PVA (degree of polymerization 500) / DMSO gel. It is a graph which shows the PVA polymerization degree dependence of the gel dielectric constant of PVA: DMSO = 1: 3 in frequency 1000Hz and 10000Hz. It is a graph which shows the FT-IR spectrum of PVC (degree of polymerization 3728) / DBA gel.

  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-like polymer device 1 according to the present invention includes a gel-like polymer material 2 having a colossal dielectric property and electrodes for applying a low-frequency bias voltage to the gel-like polymer material 2. 3 and 3. Hereinafter, each component will be described.

(Gel polymer material)
The gel-like polymer material 2 is a gel having a colossal dielectric property (giant dielectric property) in a low frequency region. The colossal dielectric has a relative dielectric constant of 1000 or more at 1 Hz and 100 or more at 10 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 low-frequency bias voltage is applied, a high dielectric constant that cannot be imagined from the dielectric constant of the insulating polymer compound that mainly constitutes 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, a 1 Hz bias voltage is applied to the gel-like polymer material 2 having a relative dielectric constant of about 10. When applied, the dielectric constant of the gel polymer material 2 can be increased to 1000 or more. In addition, the dielectric constant can be increased to 100 or more even with a bias voltage of 10 Hz. In particular, as shown in Example 3 to be described later, when a bias voltage of 1 mm Hz is applied to the gel-like polymer material 2, the relative permittivity of the gel-like polymer material 2 is increased to a giant dielectric constant close to 1 × 10 ^6. Can be increased. Further, even a bias voltage of 100 Hz can be improved to a giant dielectric constant exceeding 100.

  Colossal dielectric properties (giant dielectric properties) are known for inorganic materials, but are not known for general-purpose polymers that are low dielectric constant materials. It can be said that there is. Gel-like polymer material 2 exhibits a colossal dielectric constant, 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 the conventional polymer electrolyte system (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. The insulating polymer compound has a small dielectric constant, and usually has a relative dielectric constant of about 2 to 9. However, since the gel-like polymer material 2 obtained by gelling such an insulating polymer compound does not include an ionic material or a conductive material, energy such as heat generated by a current flowing based on the ionic material or the conductive material. The loss 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. In this way, 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 the corrosal dielectric property is changed. The gel polymer material 2 having

  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 low-frequency bias voltage 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 polymer device 1.

  The electrode 3 is connected to a power source, and 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, by applying a low-frequency bias voltage to a gel polymer material having a colossal dielectric property, Even if the molecular material is not an ion conductive polymer material or a conductive polymer material, a gel polymer device that autonomously drives in response to the bias voltage can be provided. As a result, it can be applied to new applications.

  The gel polymer device 1 includes a fine actuator element, an autonomously responsive deformable material (artificial pupil lens, etc.), a soft chuck, a fine component transfer function material, a micro switch, a micro valve, a micro pump, a Microsoft telescopic actuator (solenoid type), Examples include a microfinger, a variable focus lens, a super energy saving drive element, a high efficiency device, a flexible drive element, an artificial muscle, a deformation sensor, a pressure sensor, and the like.

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

[Experiment 1]
An aqueous solution containing 10% by mass of polyvinyl alcohol (PVA) having a degree of polymerization of 500 and an aqueous solution containing 10% by mass of dimethyl sulfoxide (DMSO) have a PVA: DMSO (mass ratio) of 1: 0.2, 1: 0. 6, 1: 1, 1: 2, and 1: 3. Each solution was cast into a polystyrene dish and dried at 35 ° C. for 2 days. Furthermore, it vacuum-dried at 20 degreeC for 8 hours, and obtained 5 types of PVA / DMSO gels. The gel-like polymer material 2 is a gel-like material that does not use polyvinyl chloride or a plasticizer, and is advantageous as the gel-like polymer material 2 with less burden on the environment.

  Furthermore, a total of 10 types of PVA / DMSO gels were obtained in the same procedure as described above using PVA having a polymerization degree of 1000 and 1700.

(Measurement)
Using the Fourier transform infrared spectrophotometer (FT-IR), the produced PVA / DMSO gel was confirmed to change the peak position of the sulfoxide group depending on the DMSO content by the attenuated total reflection method. Moreover, the dielectric constant of the produced PVA / DMSO gel was measured at all measurement frequencies using an impedance measuring device.

(result)
FIG. 2 is a graph showing an FT-IR spectrum of PVA (degree of polymerization 1000) / DMSO gel. The sulfoxide group of DMSO usually shows a peak that can be attributed to stretching motion at 1060 to 1040 cm ⁻¹ . In the PVA / DMSO gel, the stretching movement of the sulfoxide group is weakened by the hydrogen bond between the sulfoxide group of DMSO and the hydroxyl group of PVA, and the peak position is shifted to the smaller wave number as a whole.

FIG. 3 is a graph showing the dielectric constant of PVA (polymerization degree 500) / DMSO gel. The dielectric constant of PVA / DMSO gel also increased with increasing DMSO content at all measurement frequencies. In particular, in the gels of PVA: DMSO = 1: 2 and 1: 3, the dielectric constant of DMSO was higher in the high frequency region of 1000 Hz to 1 × 10 ⁶ Hz. This is probably because the polymer chain of PVA was released from the constrained state by a large amount of DMSO, making it easier for the dipole of the molecule to follow the polarity change of the electric field, and the orientation of the dipole to occur more efficiently. Conceivable.

FIG. 4 is a graph showing the PVA polymerization degree dependence of the gel dielectric constant of PVA: DMSO = 1: 3 at frequencies of 1000 Hz and 10000 Hz. The dielectric constant decreased with increasing degree of polymerization. The specific dielectric constant is 1.35 × 10 ^{4 at} 1000 Hz, 3000 at 10000 Hz at a polymerization degree of 500, 1000 at 8500 at 1000 Hz, 1000 at 1000 Hz, and 3500 at 1000 Hz at a polymerization degree of 1700. It was 500 at 10,000 Hz. This is considered to be because the mobility of DMSO hydrogen-bonded to PVA is controlled as the degree of polymerization of PVA increases. Within the range of this experiment, a polymerization degree of 500 to 1000 is preferable.

[Experiment 2]
Polyvinyl chloride (PVC) having a polymerization degree of 3728 and dibutyl adipate (DBA) were blended at a mass ratio of 1: 1, 1: 2, 1: 3, 1: 5, 1: 7, 1: 9, respectively. Stir well. Each solution was poured into a glass cell preheated at 150 ° C. An aluminum electrode is placed in advance on the opposing wall surface of the glass cell, and the injected solution is heated at 150 ° C. for 20 to 30 minutes, and plasticized PVC that is a gel-like polymer material 2 sandwiched between the electrodes Got.

  The dielectric constant was measured by the same method as in Example 1. FIG. 5 is a graph showing an FT-IR spectrum of PVC (degree of polymerization 3728) / DBA gel. As a result, when a bias voltage of 1 Hz was applied to the gel polymer material 2, the relative dielectric constant of the gel polymer material 2 could be increased to 1000 or more. Further, even with a 10 Hz bias voltage, the dielectric constant could be improved to 100 or more.

[Experiment 3]
Polyvinyl chloride (PVC) having a polymerization degree of 1140 and dibutyl adipate (DBA) were blended at a mass ratio of 1: 9, and sufficiently stirred. This 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 obtain a gelled plasticized PVC sandwiched between the electrodes.

The dielectric constant was measured by the same method as in Example 1. As a result, when a bias voltage of 1 milliHz was applied to the gel polymer material 2, the dielectric constant of the gel polymer material 2 could be increased to a giant dielectric constant close to 1 × 10 ⁶ . Further, even with a bias voltage of 100 Hz, it was possible to improve the giant dielectric constant exceeding 100.

1 Gel Polymer Device 2 Gel Polymer Material 3 Electrode

Claims (4)

  A gel-like polymer device comprising: a gel-like polymer material having a colossal dielectric property; and an electrode for applying a low-frequency bias voltage to the gel-like polymer material.   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 polymer device according to claim 1, which is any one or two or more polymer compounds selected from the group consisting of cellulose and wool.   The gel-like polymer device according to claim 1 or 2, wherein the gel-like polymer material has a relative dielectric constant of 1000 or more at 1 Hz and 100 or more at 10 Hz.   A step of preparing an insulating polymer compound in a gel state and preparing a gel-like polymer material having a colossal dielectric property; a step of forming an electrode for applying a low-frequency bias voltage to the gel-like polymer material; A method for producing a gel-like polymer device, comprising:

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