JP4545484B2 - Manufacturing method of plastic molded products - Google Patents

Description

  The present invention relates to a technology for manufacturing a plastic molded article that can be applied to a micro structure and a micro structure of μm order and nm order.

Conventionally, for example, the following methods are known as methods for producing plastic molded products (synthetic resin products).
(1) A method of obtaining a plastic molded product by filling a mold with a molten resin and then cooling the molten resin as in injection molding (see Patent Document 1)
(2) A method of forming a thin film component having a two-dimensional shape corresponding to a mask by partially removing the thin film formed of a synthetic resin on the surface of the substrate using the photoresist formed thereabove as a mask ( (Photolithography: see FIG. 21)
(3) When photolithography is performed using synchrotron radiation having strong straightness as in the LIGA process, a concavo-convex molded product having a high aspect ratio can be obtained. A mold is manufactured by molding, and the mold is heated and pressed against a thermoplastic resin (hot embossing) to replicate a plastic molded product having a shape corresponding to the concave-convex molded product (see FIG. 22).
(4) Like rapid prototyping, three-dimensional CAD data of a product is sliced thinly into slices and converted into contour data, and uncured photocurable resin is divided into thin layers based on the contour data. A method of obtaining a three-dimensional shape of a plastic molded article by sequentially irradiating a laser beam and curing, and removing uncured resin after completion of lamination of the cured portions of each thin layer (see FIG. 23)
However, although the method (1) is excellent in mass productivity, it is not suitable for trial production and has a problem that it is difficult to form a fine shape. On the other hand, in the method (2), the thickness of the molded product can be reduced to about several tens of μm at the maximum, and expensive manufacturing equipment is required, and waste processing accompanying development processing is necessary. Further, in the method (3), the synchrotron radiation apparatus is very expensive, and even if the mold is outsourced, it is costly. The method (4) is a method for producing a three-dimensionally complicated fine shape. However, it takes a lot of time to manufacture one product, and there is a problem that mass productivity is very bad particularly when a product having a simple area and a large area is produced.
JP-A-5-185464

  The present invention has been made in view of the above problems, and provides a plastic molded product manufacturing method, a manufacturing apparatus, and a plastic molded product manufactured by the manufacturing method capable of easily molding even a fine shape. The challenge is to do.

In order to solve the above-mentioned problems, the present invention provides a mixed solution supplying step of filling a mixed solution composed of at least two types of liquids that are insoluble and have different dielectric constants into an electric field application cell in which electrodes are arranged to face each other . Forming a layer of the first liquid of at least two kinds of liquids constituting the mixed liquid on the first electrode surface constituting the electric field application cell; and configuring the electric field application cell. A step of forming a layer of a second liquid of at least two kinds of liquids constituting the mixed liquid on the second electrode surface, and the first electrode surface on which the first liquid is formed And a step of bonding the second electrode surface on which the second liquid is formed to produce an electric field application cell in which the mixed liquid is formed in layers, and an electric field is applied between the electrodes. Of the liquid constituting the liquid mixture An electric field applying step of collecting a liquid having a high dielectric constant so as to extend in the electric field direction and forming a bridge structure connecting the electrodes, and at least one of the liquids constituting the mixed liquid is an uncured curable resin And a method for producing a plastic molded product in which the curable resin is cured after the bridge structure is formed.

Further, in the following method for producing a plastic molded product, after forming a pattern of a substance that repels the high dielectric constant liquid on the electrode surface, droplets are formed by depositing the high dielectric constant liquid. It is characterized by that.

The method of manufacturing a plastic molded article, mixture of at least two kinds of liquid dielectric constant different mutually insoluble, the mixture supplying step in which the electrode is filled into field application cell that is disposed to face the Forming, on the first electrode surface constituting the electric field application cell, as a droplet, a high dielectric constant liquid having the highest dielectric constant among at least two kinds of liquids constituting the mixed liquid; and applying the electric field Forming a layer of a liquid other than the high dielectric constant liquid out of at least two kinds of liquids constituting the liquid mixture on the second electrode surface constituting the cell for the cell; A step of bonding the electrode surface of 1 and the second electrode surface on which the layer is formed to produce an electric field application cell filled with the mixed solution , and applying an electric field between the electrodes. Composition of the mixture An electric field application step of collecting a liquid having a high dielectric constant so as to extend in the direction of the electric field and forming a bridge structure connecting the electrodes, and at least one of the liquids constituting the mixed liquid is uncured The curable resin is cured after the bridge structure is formed .

The method of manufacturing a plastic molded article, mixture of at least two kinds of liquid dielectric constant different mutually insoluble, the mixture supplying step in which the electrode is filled into field application cell that is disposed to face the On the first electrode surface constituting the electric field application cell, a step of forming, as a droplet, a high dielectric constant liquid having the highest dielectric constant among at least two kinds of liquids constituting the mixed liquid , The step of forming the liquid other than the high dielectric constant liquid in a layered manner among at least two kinds of liquids constituting the mixed liquid and the step of bonding the second electrode surface constituting the electric field application cell together A step of producing a cell for applying an electric field filled with a liquid, and collecting a liquid having a high dielectric constant so as to extend in the electric field direction among the liquids constituting the mixed liquid by applying an electric field between the electrodes. while And a electric field application step of forming a bridge structure connecting said at least one liquid mixture constituting the liquid is a curable resin uncured, characterized by curing the curable resin after formation of the bridge structure And

Here, the curable resin may be an active energy ray curable resin that is cured by irradiation with an active energy ray .

The active energy ray curable resin may be an ultraviolet curable resin that is cured by irradiation with ultraviolet rays .

Further, the curable resin may be a thermosetting resin that is cured by heating .

The mixed liquid may be composed of two types of liquids that are insoluble and have different dielectric constants .

Further, of the two kinds of liquids constituting the mixed liquid, the liquid having a high dielectric constant is an uncured curable resin, and after the curable resin is cured, the liquid other than the liquid having the high dielectric constant is removed. Can do.

Further, the liquid other than the liquid having a high dielectric constant constituting the liquid mixture is an uncured curable resin, and the liquid having a high dielectric constant can be removed after the curable resin is cured .

Further, the liquid having a high dielectric constant constituting the liquid mixture is the first uncured curable resin, and the liquid other than the liquid having the high dielectric constant is different from the first uncured curable resin. It is a second uncured curable resin, and after the first curable resin is cured, the second curable resin can also be cured .

The liquid having a high dielectric constant is an uncured curable resin, and the liquid other than the liquid having a high dielectric constant is a melt of a hot-melt material that melts by heating, and the curable resin is cured. Later, the melt of hot melt material can be cured .

Further, the liquid having a high dielectric constant is an uncured curable resin, and the liquid other than the liquid having a high dielectric constant is a melt of a hot melt substance melted by heating, and the melt of the hot melt substance is After being cured, the curable resin can be cured .

The liquid other than the liquid having a high dielectric constant is an uncured curable resin, and the liquid having a high dielectric constant is a melt of a hot-melt material that melts by heating, and the curable resin is cured. Later, the melt of hot melt material can be cured .

Further, the liquid other than the liquid having a high dielectric constant is an uncured curable resin, and the liquid having a high dielectric constant is a melt of a hot melt substance that melts by heating, and the melt of the hot melt substance is The curable resin can also be cured after curing .

The electric field applied between the electrodes may be an alternating electric field .

Furthermore, the electric field applied between the electrodes may be a direct current electric field .

  According to the present invention, since the bridge structure obtained by utilizing the electrorheological effect described below is fixed by the curable resin, it is possible to easily form a fine shape on the order of μm or nm.

  That is, for example, if an attempt is made to produce a highly perpendicular structure with a negative resist by photolithography (patterning of a negative resist) shown in FIG. 21, the sample must be irradiated with ultraviolet rays through a photomask with a pattern shape. Therefore, the influence of the contact between the sample and the photomask, the straightness of the ultraviolet light, the incident angle, etc. becomes remarkable, and very expensive equipment is required.

  On the other hand, in the present invention, a liquid having a high dielectric constant due to the electrorheological effect is automatically fixed in the electric field direction by so-called curable resin, so that manufacturing conditions such as light straightness and incident angle are used. Therefore, a highly accurate plastic molded product can be obtained very easily at low cost.

  In particular, when filling an electric field application cell without dispersing at least two kinds of liquids constituting a mixed liquid, when the bridge structure is formed by applying an electric field, the bridge structure cannot be formed and the dielectric constant is reached. A high liquid is not present in the liquid as a droplet. That is, it is possible to manufacture a plastic molded article in which the region where the high dielectric constant liquid exists is defined.

  The plastic molded article thus obtained can be applied to optical waveguides, diffraction grating optical elements, wave plates, spacers, microcells, and the like.

In the case of forming the liquid droplets, it is possible to selectively form a bridge to the location.

Further, a curable resin having high permittivity liquids, if so other liquid after curing has been removed, it is possible to obtain a highly accurate columnar cured resin molded product.

On the other hand, a permittivity of high liquid curable resin other than the liquid, if The other liquid after curing has been removed, it is possible to obtain a curable resin molded article having a high-precision perforated structure .

Additionally, mixed-liquid is composed two kinds of curable resin, or, if so mixture comprises a curable resin and a heat melting material, the other either of which constitutes a columnar portion constitutes the peripheral portion Thus, a plastic molded product having anisotropy between the columnar portion and the peripheral portion can be obtained.

  According to the present invention, a plastic molded product having a fine shape can be easily molded.

  The best mode for carrying out the present invention will be described with reference to the drawings.

FIG. 1 shows an outline of a method for producing a plastic molded product according to this embodiment. In this manufacturing method, first, at least two types of liquids (at least one of which is an uncured curable resin) that are insoluble and have different dielectric constants are layered on the electrode surface or formed as droplets on the electrode surface. Or a film formed on a layer or a droplet and placed at a predetermined position (step 1 (denoted as S.1 in FIG. 1; the same applies hereinafter)).

  And this liquid mixture is set to an electric field application apparatus (cell for electric field application) (step 2). Next, an electric field is applied to the mixed solution by an electric field applying cell to form a bridge structure (step 3). In this state, the curable resin is cured to obtain a plastic molded product (step 4).

  By the way, the bridge structure in Step 3 refers to a form in which liquids having a high dielectric constant among the two types of liquids gather so as to extend in the direction of the electric field, and the liquids connect between the electrodes of the electric field application cell. Such a bridge structure is realized by using the ER (Electro Rheology) effect.

  Here, the ER effect is a particle (solid-liquid system: see, for example, EN da Andrade et al., Nature, 143, p.3610, 1939) or liquid (liquid-liquid) in the dispersion solvent. System: For example, K. Tajiri et al., J. Rheol., 41 (2), p.335, 1997) is dispersed (in the case of a liquid-liquid system, it is dispersed as fine droplets by stirring.) By applying an electric field (V / μm) to this, particles having a high dielectric constant or liquid droplets are connected, or the liquid droplet is deformed in the direction of the electric field to connect the electrodes ( This is a phenomenon in which the viscosity increases as a result (see FIG. 2).

  In addition, as shown in FIG. 3, the dispersion solute (high dielectric constant liquid) and the dispersion solvent (low dielectric constant liquid), which are liquids constituting the mixed liquid, can be separately formed into layers. In this method, a high dielectric constant liquid and a low dielectric constant liquid are respectively formed on two electrode substrates, and the two are bonded together so that the liquid contacts after the film formation. By applying an electric field to the high dielectric constant liquid uniformly formed without dispersing the liquid constituting the liquid mixture in this way, the bridge structure without dispersing the high dielectric constant liquid in the liquid due to the ER effect. Can be formed.

  In addition, as shown in FIG. 4, a droplet of a dispersed solute (high dielectric constant liquid) can be formed on at least one electrode surface. In this method, liquid droplets of a high dielectric constant liquid are formed only on the electrode surface, and by applying an electric field thereto, each liquid droplet extends in a direction parallel to the electric field by the ER effect and connects the electrodes. A bridge structure is formed.

  ER fluid (solid-liquid dispersion system, liquid-liquid system) that expresses the ER effect has been studied so far. Conventionally, the ER effect has an increase in viscosity due to the formation of a bridge structure upon application of an electric field, and the viscosity. It was only used for reversible changes in liquid and fluid properties, and was used for changes in liquid or fluid properties.

  On the other hand, in this embodiment, a plastic molded product that is solid using the ER effect with a view to forming a plastic molded product having a fine shape / micro shape or a device of a plastic molded product having a function due to the structure. Stabilization of the structure. That is, in this embodiment, at least one of at least two liquids constituting a liquid-liquid ER solution (dispersion solution) is used as a liquid precursor of a curable resin, and an electric field is applied to the ER solution to form a bridge structure. Then, the curable resin is cured to fix the bridge structure. Thereby, it is possible to easily produce a plastic molded product having a regular pattern structure of μm order and nm order.

  Hereinafter, more specific examples will be described.

[Fluorine oil-UV curable resin system]
Disperse solute (low concentration, high concentration in dispersion) against fluorinated oil (fluorine-containing oil: Daikin Industries, demnum S-65) as dispersion solvent (high concentration in dispersion, low dielectric constant) Add 2 wt% (mass%) of UV curable resin (dielectric liquid) (Henkel Japan Co., Ltd., Loctite3311) and stir for 6 minutes at 600 rpm with a rotating blade type stirrer (long axis length of stirring blade 17 mm) did. As a result, a dispersion liquid (mixture) in which the ultraviolet curable resin was dispersed as droplets of about 10 μmφ was obtained, and this dispersion liquid was supplied to the electric field application cell 1 shown in FIG.

  The electric field applying cell 1 is formed by arranging rectangular copper electrodes 3 and 4 having a thickness of 1 mm on the surface of the glass substrate 2 in parallel so as to maintain a separation distance of 1.5 mm. A predetermined voltage is applied between 3 and 4. The dispersion liquid was filled in the facing space 6 between the copper electrodes 3 and 4 (FIG. 6A), and the dispersion liquid overflowing to the side of the facing space 6 was removed by wiping. The dispersion state of the liquid droplets in the dispersion liquid is stable over time. In FIG. 6, reference numeral 7 represents the dispersion liquid, reference numeral 8 represents the dispersion solvent, and reference numeral 9 represents the liquid droplets.

  Next, when an AC electric field of 1.33 V / μm (50 Hz, 2 kV AC voltage) is applied between the copper electrodes 3 and 4, the droplets of the ultraviolet curable resin are deformed so as to extend in the direction of the electric field, and adjacent droplets are deformed. By gathering and assimilating each other, a bridge structure 11 in which an aggregate (bridge) 10 of droplets 9 connects between the copper electrodes 3 and 4 was obtained (FIG. 6B). FIG. 7 shows a state of the bridge 10 when 15 seconds have elapsed after the start of electric field application, where the bridge 10 has a diameter of about 10 μmφ.

Subsequently, 100 mW / cm ² of ultraviolet light was irradiated for 3 minutes with the light source 12 such as a mercury lamp while this electric field application state was continued, and when the application of the electric field was stopped, the bridge structure was maintained by curing of the ultraviolet curable resin. (FIG. 6C). In FIG. 6, the bridge structure after curing is denoted by reference numeral 13 in order to distinguish it from the bridge structure 11 before curing, and the bridge in the bridge structure 13 is denoted by numeral 14 in order to distinguish it from the bridge 10 in the bridge structure 11. For comparison, when the application of an electric field is stopped without irradiating this material system with ultraviolet rays, the bridge 10 made of uncured curable resin is broken in a few seconds, and the curable resin is a large liquid of several hundred μmφ. Drops were again dispersed in the dispersion solvent 8.

  The fine columnar body (bridge 14) remaining between the copper electrodes 3 and 4 is obtained by immersing the electric field applying cell 1 in which the bridge structure 13 is formed in a fluorine-based solvent such as a fluorine-substituted hydrocarbon and removing the fluorine-based oil. ) Was obtained as a plastic molded product (FIG. 6D).

  By the way, when trying to manufacture a minute columnar body such as the bridge 14 by injection molding, it is necessary to manufacture a mold having a through hole, fill the hole with a molten resin, and release the mold, but the hole diameter is 1 mm. In the following orders, even if the molten resin is injected from both sides of the through hole, the filling will be insufficient, and when it is arrayed, the dispersion of the filling point will increase, and even if it can be filled, the molten resin will be cured Since it is difficult to release the mold without breaking the shape later, the feasibility is poor.

  On the other hand, in the method of manufacturing a plastic molded product according to the present embodiment, a state in which a liquid having a high dielectric constant automatically extends in the direction of the electric field due to the ER effect is fixed very easily by fixing the ultraviolet curable resin. In addition, the plastic molded product can be manufactured at low cost.

[Fluorine oil-UV curable resin system]
In this example, the same process as in Example 1 was performed except that the applied electric field was a DC electric field of 1.0 V / μm, and a plastic molded product substantially similar to Example 1 was obtained.

[Silicone oil-UV curable resin system]
In this example, 500 cSt silicone oil (Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone KF-96-500CS) was used as the dispersion solvent, and the applied electric field was 1.0 V / μm AC electric field (50 Hz, 1.5 kV AC voltage). The bridge structure 11 shown in FIG. 8 was obtained by applying an electric field in the same manner as in Example 1. In this example, the application of an electric field caused the droplets to associate with each other due to the Coulomb attractive force caused by the polarization of the droplets of the ultraviolet curable resin, and the diameter of the bridge 10 was about 300 μmφ, which was thicker than in Example 1.

  After the bridge 10 is cured by ultraviolet irradiation to form a large-sized plastic molded product, the electric field applying cell 1 is dipped in silicone oil and low-viscosity silicone oil having the same physical properties as the dispersion solvent, and ethanol in this order. Was removed.

[Silicone oil-UV curable resin system]
In this example, the same process as in Example 3 was performed except that the applied electric field was a DC pulse electric field of 1.0 V / μm and 1 kHz, and a plastic molded product substantially similar to Example 3 was obtained.

[UV curable resin-UV curable resin system]
In this example, 2% by weight of a liquid crystal type UV curable resin (Dainippon Ink and Chemicals UCL-011) was added as a dispersion solute to the UV curable resin (NOLAND NOA60) as a dispersion solvent, and 600 rpm with the above stirrer. For 10 minutes. As a result, a liquid dispersion (mixed liquid) in which a liquid crystal ultraviolet curable resin was dispersed as droplets of about 10 μmφ was obtained, and this liquid dispersion was supplied to the electric field application cell 1. In the electric field application cell 1, the dispersion liquid overflowing to the side of the facing space 6 was wiped away and the dispersion state of the liquid droplets in the dispersion liquid was stable over time.

  Next, when an AC electric field of 1.5 V / μm (50 Hz, AC voltage of 2.25 kV) is applied between the copper electrodes 3 and 4 of the electric field applying cell 1, the liquid crystal UV curable resin droplets are aligned in the electric field direction. As a result, the bridge structure as shown in FIG. 6B was obtained.

Subsequently, 100 mW / cm ² of ultraviolet light was irradiated for 3 minutes from the light source 12 while this electric field application state was continued, and when the application of the electric field was stopped, the curing of both the ultraviolet curable resin of the dispersion solvent and the dispersed solute resulted in FIG. The plastic molding 15 shown was obtained. In FIG. 9, reference numeral 16 denotes a fine bridge portion formed by hardening the dispersed solute, and reference numeral 17 denotes a matrix portion formed by hardening the dispersion solvent. For example, the bridge portion 16 is a transparent body and the matrix portion 17 is an opaque body. By doing so, the plastic molded product 15 can be used as a light guide component.

  In addition, when the central curing wavelength of the ultraviolet ray for curing the ultraviolet curable resin as the dispersion solvent is different from the central curing wavelength of the ultraviolet ray for curing the ultraviolet curable resin as the dispersion solute, both wavelengths are included. The dispersion solvent and the dispersion solute may be individually cured by irradiating two light sources emitting different wavelengths separately as described above by light rays.

[Hot-melting resin-UV curable resin system]
In this example, polypropylene (Idemitsu Petrochemical IDEMITSU PP J-2021GR) pellets as a dispersion solvent were pulverized by a pulverizer, heated to 170 ° C. and melted, and the melt was stirred. However, 2 wt% of an ultraviolet curable resin (Dainippon Ink and Chemicals UCL-011) as a dispersion solute was added. Further, stirring was continued until the ultraviolet curable resin droplets reached about 10 μmφ to prepare a dispersion (mixed liquid) in which the ultraviolet curable resin droplets were dispersed in the molten resin. Also in this dispersion, the dispersion state of the droplets was stable over time even after stirring was stopped.

  Next, the electric field applying cell 1 is placed on a hot plate (not shown) heated to 170 ° C., the dispersion is supplied to the facing space 6, and a 1.0 V / μm direct current is applied between the copper electrodes 3 and 4. A field was applied. Then, the droplets of the ultraviolet curable resin were assimilated while continuing in the direction of the electric field, thereby obtaining a bridge structure as shown in FIG.

Subsequently, while the electric field application state was continued, the light source 12 was irradiated with 100 mW / cm ² of ultraviolet rays for 3 minutes to stop the application of the electric field. As a result, the bridge structure was maintained by curing of the ultraviolet curable resin. Further, by stopping the heating of the electric field application cell 1 by the hot plate, the molten alkali resin was subjected to cooling and curing, and a plastic molded product having a bridge portion and a matrix portion as shown in FIG. 9 was obtained.

  In this example, there was no inhibition of curing of the UV curable resin due to UV absorption of the acrylic resin, and the acrylic resin was first cooled and cured before being irradiated with UV light to cure the UV curable resin. Also good.

[Silicone oil-thermosetting resin system]
In this example, an electric field was applied in the same manner as in Example 3 except that a thermosetting resin (NOLAND NOA83H) was used as a dispersion medium, and a bridge structure as shown in FIG. 6B was obtained.

  Subsequently, the voltage application cell 1 was heated at 130 ° C. for 10 minutes while the electric field application state was continued, and the application of the electric field was stopped. As a result, the bridge structure was maintained by the curing of the thermosetting resin, and FIG. A plastic molded product as shown in FIG.

  After the thermosetting resin was cured, the electric field applying cell 1 was immersed in a silicone oil and ethanol having the same physical properties as the dispersion solvent and low viscosity in this order, thereby removing the silicone oil as the dispersion solvent.

[Ultraviolet curable resin-thermosetting resin system]
In this example, an electric field was applied in the same manner as in Example 7 except that a thermosetting resin (NOLAND NOA83H) was used as the dispersion solvent and an ultraviolet curable resin (Dainippon Ink and Chemicals UCL-011) was used as the dispersion solute. A bridge structure as shown in FIG. 6B was obtained.

  Subsequently, the voltage application cell 1 was heated at 130 ° C. for 10 minutes while this electric field application state was continued, and the application of the electric field was stopped. As a result, the bridge structure was maintained by the curing of the thermosetting resin. Furthermore, the ultraviolet curable resin was cured by irradiation with ultraviolet rays, and a plastic molded article having a bridge portion and a matrix portion as shown in FIG. 9 was obtained. In addition, after irradiating an ultraviolet-ray previously and hardening an ultraviolet curable resin, a thermosetting resin may be heated and hardened.

[Modification of electric field application cell]
In this example, the dispersion prepared in the same manner as in Example 1 was supplied to the electric field application cell 18 shown in FIG. The electric field applying cell 18 includes glass substrates 19 and 20 and a power source 21 that are arranged to face each other in the vertical direction.

  A patterned electrode 22 is formed on the lower surface of the glass substrate 19 by vapor deposition of ITO (Indium Tin Oxide), and a patterned electrode 23 is formed on the upper surface of the glass substrate 20 by vapor deposition of ITO. On the upper surface of the glass substrate 20, rectangular glass spacers 24, 25 and 26 and an insulating spacer 27 are provided so as to be positioned above the electrode 23. The glass spacers 24, 25, 26 are arranged in a U shape in plan view, and the insulating spacer 27 is arranged in close contact with the glass spacers 24, 26 so as to close the U shape, and thereby above the electrode 23. Is formed with an electric field chamber 28 surrounded by spacers 24, 25, 26 and 27 on all sides. Here, the glass spacers 24, 25, and 26 are fixed to the upper surface of the glass substrate 20 with hot wax (adhesive that melts by heat), and the insulating spacer 27 is detachably installed on the upper surface of the glass substrate 20. The height is set to 1.0 mm. Moreover, ITO does not need to be vapor-deposited in a pattern on a part of the surfaces of the glass substrates 19 and 20 as described above, and may be vapor-deposited on the entire surfaces of the glass substrates 19 and 20.

  The dispersion liquid is filled in the electric field chamber 28 on the glass substrate 20, and the glass substrate 19 is placed on the spacers 24, 25, 26 and 27 so as to be covered with the electrode 22. At this time, the dispersion overflowing from the electric field chamber 28 is wiped away and the spacers 24, 25, 26, 27 are used to separate the glass substrates 19, 20 (electrodes 22, 23) at a predetermined distance (1.0 mm). ).

  Next, when a 1 V / μm AC electric field (50 Hz, 1 kV AC voltage) is applied between the electrodes 22 and 23 by the power source 21, the droplets of the ultraviolet curable resin are deformed so as to extend in the electric field direction (vertical direction). Neighboring droplets gathered and assimilated, thereby obtaining a bridge structure in which a bridge having a diameter of about 10 μmφ extends in the vertical direction.

  Subsequently, while this electric field application state is continued, ultraviolet rays are irradiated to the inside of the electric field chamber 28 through the glass substrates 19 and 20 and the electrodes 22 and 23 or through the glass spacers 24, 25 and 26, and then an electric field is applied. Was stopped, the bridge structure was maintained by the curing of the UV curable resin, and the dot pattern observed through the glass substrates 19 and 20 and the electrodes 22 and 23 (dot pattern with dots at the upper and lower ends of the bridge) did not change. .

  Then, the insulating spacer 27 was removed and the oil adhering to the bridge hardened with ethanol that did not dissolve the ultraviolet curable resin was washed to obtain a columnar body that appeared at random on the surface to which an electric field was applied as a plastic molded product.

[Production example of plastic molded product with perforated structure]
In this example, glycerin (Kanto Chemical Reagent), which has a high dielectric constant, is added to the low-dielectric constant UV curable resin (NOLAND NOA60) at a ratio of 2% by weight, and the oil is about 10 μmφ by stirring this. A dispersion liquid (mixed liquid) dispersed as droplets was prepared, and this dispersion liquid was supplied to the electric field application cell 29 shown in FIG.

  The electric field application cell 29 is formed by placing parallel rectangular copper electrodes 31 and 32 having a thickness of 1 mm and a length of 10 mm on the surface of the glass substrate 30 so as to maintain a separation distance of 2.0 mm. Insulating spacers 33 and 34 having a thickness of 1 mm that are in close contact with the end faces in the length direction of 31 and 32 are installed so as to be orthogonal to the copper electrodes 31 and 32. An electric field chamber 35 surrounded by 32 and insulating spacers 33 and 34 is formed. A predetermined voltage is applied between the copper electrodes 31 and 32 by a power source 36.

  When the dispersion liquid is filled in the electric field chamber 35 and an AC electric field (50 Hz, 3 kV AC voltage) of 1.5 V / μm is applied to the electric field chamber 35 (between the copper electrodes 31 and 32), droplets of glycerin are formed. A bridge structure as shown in FIG. 6B was obtained in the electric field direction. Subsequently, the ultraviolet curable resin was cured by irradiating ultraviolet rays while continuing this electric field application state, and a bridge structure 37 as shown in the upper diagram of FIG. 12 was obtained. In FIG. 12, reference numeral 38 denotes a bridge portion made of oil, and reference numeral 39 denotes a matrix portion made of ultraviolet curable resin. By hardening the matrix portion 39, liquid oil forming the bridge portion 38 is held in a columnar shape. ing.

  Next, the bridge structure 37 and the glass substrate 30 are cut out by a dicing saw (not shown), and the cut-out bridge structure with the glass substrate is subjected to ultrasonic cleaning in ethanol. A plastic molded article 41 having a honeycomb-shaped hole 40 as shown was obtained. The plastic molded article 41 has a small-diameter cavity extending only in a single direction, but the manufacture of such a product is extremely difficult by various conventional manufacturing techniques.

[Example of filling liquid mixture in which two electrodes are separately formed and bonded]
In this example, two types of liquids (high dielectric constant liquid and low dielectric constant liquid) constituting the mixed liquid were respectively disposed on the electrodes 42 and 44 by film formation.

  For the electrodes 42 and 44, an electrode substrate on which a conductive material (Al, Ni, Cu, ITO, etc.) was formed was used. For the two electrodes 42 and 44, a high dielectric constant liquid (UV curable resin: Henkel Japan Co., Ltd., Loctite 3311) is formed on one electrode 42 surface, and a low dielectric constant liquid (silicone) is formed on the other electrode 44 surface. Oil: Shin-Etsu Chemical Co., Ltd. and Shin-Etsu Silicone KF-65-1000CS) were formed.

  In FIG. 13, the formed layered high dielectric constant liquid is represented by reference numeral 43, and the formed layered low dielectric constant liquid is represented by reference numeral 45. The two electrode substrates 42 and 44 formed with the high dielectric constant liquid and the low dielectric constant liquid are bonded so that the respective liquids are in contact with each other, so that the mixed liquid is layered between the electric field application electrodes (electric field application cell). Formed. When a DC electric field of 1.0 V / μm is applied to the mixed liquid formed in this layer form by the power supply 46, the high dielectric constant liquid extends in the electric field direction in a part of the bridge 47 connecting the electrodes 42 and 44. A bridge structure 48 having was formed.

  In the example shown in FIG. 14, a high dielectric constant solution is formed on each of the electrodes 42 and 44, and a low dielectric constant solution is further formed on one electrode 44. Then, the electrode 42 formed with the high dielectric constant liquid and the electrode 44 formed with the high dielectric constant liquid and the low dielectric constant liquid were bonded together so that the liquid was in contact therewith.

  In this embodiment, since two types of liquids constituting the mixed liquid are formed in layers on the electrodes 42 and 44, the high dielectric constant liquid is not dispersed and does not exist as droplets in the mixed liquid.

[Example of filling a mixed solution in which a single electrode is sequentially formed and bonded together]
In this example, two types of liquids (high dielectric constant liquid and low dielectric constant liquid) constituting the mixed liquid were sequentially arranged on one electrode 42 by film formation.

  For the electrodes 42 and 44, an electrode substrate on which a conductive material (Al, Ni, Cu, ITO, etc.) was formed was used. First, a high dielectric constant liquid (UV curable resin: Henkel Japan Co., Ltd., Loctite3311) is formed on the electrode 42 surface of one substrate, and a low dielectric constant liquid (silicone oil: Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone) is formed thereon. KF-65-1000CS) was formed.

  Then, the other electrode 44 substrate was bonded onto the low dielectric constant liquid layer 45 to form a mixed liquid in a layered manner between the electric field application electrodes (electric field application cell). When a DC electric field of 1.0 V / μm was applied to the mixed liquid formed in this layer form by the power supply 46, the high dielectric constant liquid extended in the electric field direction in some places as in Example 11, and the electrodes 42, A bridge structure 48 connecting the 44 was formed.

  Further, in the example shown in FIG. 16, after a high dielectric constant liquid layer 43 and a low dielectric constant liquid layer 45 are laminated on one electrode 42, a high dielectric constant liquid layer 43 is further formed thereon. . Then, another electrode 44 was bonded onto the uppermost layer 43 of the high dielectric constant liquid.

[Filling example of mixed liquid in which droplets of high dielectric constant liquid are formed on the electrode surface and bonded together]
In the present example, among the two types of liquids constituting the mixed liquid, the high dielectric constant liquid was formed as droplets on the electrode surface, and the low dielectric constant liquid was disposed by film formation.

  For the electrodes 49 and 53, an electrode substrate on which a conductive material (Al, Ni, Cu, ITO, etc.) was formed was used. Then, a high dielectric constant liquid (ultraviolet curable resin: Henkel Japan Co., Ltd., Loctite3311) is discharged onto the surface of the electrode 49 of one substrate by a discharger 51 (Musashi Engineering, SMP-III), and a droplet having a diameter of about 50 μm. 50 was formed. An ink jet printer head can also be used for the discharger 51.

  On the electrode 49 on which the droplet 50 of the high dielectric constant liquid is formed, a low dielectric constant liquid film is formed to form a low dielectric constant liquid layer 52. And the other electrode 53 board | substrate is bonded together on it (refer FIG. 17).

  When the liquid mixture is supplied to the electric field application cell as described above, the liquid mixture can be filled between the electric field application electrodes in a state where the high dielectric constant liquid exists as droplets 50 on the surface of the electrode 49. When a DC electric field (1.0 V / μm) is applied to the mixed solution from the power source 54, the high dielectric constant solution extends in the direction of the electric field in a part of the bridge, and has a bridge 55 having a bridge 55 that connects between the electrodes 49 and 53. A structure 56 could be formed.

  In this embodiment, since the liquid droplet 50 of the high dielectric constant liquid is formed on the electrode surface without interposing another liquid, the liquid droplet is separated from the electrode surface as the high dielectric constant liquid is dispersed in the mixed liquid. Never existed. In addition, since the bridge 55 can be formed at the position where the droplet 50 is disposed, the bridge structure 56 can have a desired pattern structure.

  FIG. 18 shows a modification of the method of filling the liquid mixture into the electric field application cell for forming the high dielectric constant liquid droplets.

  In FIG. 18A, a high dielectric constant liquid droplet 50 is formed on one electrode 49 and a low dielectric constant liquid film is formed on the other electrode 53 to form a low dielectric constant liquid layer 52. Then, the liquid mixture is filled into the electric field application cell by bonding them together.

  In FIG. 18B, droplets 50 of a high dielectric constant liquid are formed on the surfaces of two electrodes 49 and 49, respectively, and the other portions are filled with a low dielectric constant liquid formed.

  Further, FIG. 18C does not directly form a high dielectric constant liquid droplet 57 on the surface of the electrode 55 of the electric field application cell, but an intermediate layer 56 such as a plastic sheet is formed on the surface of the electrode 55. This is a method of forming a high-permittivity liquid droplet 57 after placement. A layer 58 of a low dielectric constant liquid is disposed between the electrodes 55 and 55. Here, the intermediate layer 56 and the electrode 55 may be in close contact with each other or a gap may exist.

[Example of forming liquid droplets of high dielectric constant on the electrode surface by the surface treatment agent]
In this example, a high-dielectric-constant liquid droplet was formed on the electrode surface using a surface treatment agent having a property of repelling a high-dielectric-constant liquid. FIG. 19 shows a pretreatment process until the high dielectric constant liquid is arranged, and FIG. 20 shows a posttreatment process until the electric field application cell is filled with the mixed liquid.

  The electrode 60 is made of an electrode substrate on which a conductive material (Al, Ni, Cu, ITO, etc.) is formed, and a photoresist (Tokyo Ohka Kogyo: TSMR-8900) is spin-coated on the electrode surface. (FIG. 19A), a remaining square pattern (photoresist 61) with a side of 50 μm in plan view was formed on the photoresist by photolithography (FIG. 19B). Then, after a surface treatment agent 62 (release agent, for example, Gelest Aquaphobe CF) is formed thereon (FIG. 19C), the remaining photoresist 61 is removed with acetone, so that a square in plan view is obtained. The surface treatment agent 62 pattern which has the shape-like opening 63 was formed (FIG.19 (D)).

  When a high dielectric constant liquid (ultraviolet curable resin: Henkel Japan Co., Ltd., Loctite 3311) is formed on the surface of the electrode 60 having the opening 63 having a square shape in plan view, the high dielectric constant liquid is applied to the opening 63 of the surface treatment agent. It was localized as a droplet 64 (from the lower left figure to the middle figure in FIG. 20). Alternatively, a high-dielectric-constant liquid droplet 64 may be formed in the surface treatment agent opening 63 by a discharger 65 (from the upper left of FIG. 20 to the central view). As a result, a droplet 64 having a diameter of about 100 μm could be formed on the surface of the electrode 60.

  As described in the thirteenth embodiment, various methods can be adopted for the process after the droplet 64 of the high dielectric constant liquid is formed on the electrode 60 surface. The upper right diagram of FIG. 20 shows a low dielectric constant liquid layer 65 and a high dielectric constant liquid layer 67 between the electrode 60 on which the high dielectric constant liquid droplet 64 is formed as described above and the other electrode 66. Is an example of forming. 20 shows an example in which a low dielectric constant liquid layer 65 is formed between the electrode 60 on which the high dielectric constant liquid droplets 64 are formed and the other electrode 66. Further, the lower right diagram of FIG. 20 shows an example in which two electrodes 60, 60 each having a high dielectric constant liquid droplet 64 formed thereon are used, and a low dielectric constant liquid layer 65 is formed between the electrodes 60, 60. is there.

  As mentioned above, although the form for implementing this invention was demonstrated, this invention is not restricted to the form mentioned above, For example, although the liquid mixture which consists of two types of liquid was illustrated in the said form, curable resin is included. A mixed liquid composed of three or more kinds of liquids may be used.

  Moreover, although the combination of ultraviolet curable resin was illustrated as a combination of two types of curable resin which comprises a liquid mixture with the said form, even if it combines thermosetting resins, or ultraviolet curable resin and thermosetting resin, May be combined.

  Furthermore, although the ultraviolet curable resin is exemplified as the active energy ray curable resin in the above embodiment, an electron beam curable resin that is cured by an electron beam may be used.

It is a flowchart which shows the manufacturing method of the plastic molded product which concerns on the best form for implementing invention. It is explanatory drawing which shows the electrorheological effect. It is explanatory drawing which shows the electrorheological effect when the liquid which comprises a liquid mixture is formed in layers. It is explanatory drawing which shows the electrorheological effect when the droplet of a high dielectric constant liquid is formed on an electrode surface. It is explanatory drawing which shows the cell for electric field application. In the process of manufacturing a plastic molded product, (A) shows a state in which a dispersion is supplied to an electric field application cell, (B) shows a state in which an electric field is applied to the dispersion, and (C) shows a state in which a curable resin is cured. (D) is explanatory drawing which shows the state where the finishing process was performed and the plastic molded product was obtained. 2 is a photograph showing an electric field application state in Example 1. FIG. 10 is a photograph showing an electric field application state in Example 3. It is explanatory drawing which shows the plastic molded product obtained in Example 5. FIG. The other example of the cell for electric field application is shown, (A) is the explanatory view which shows the state which removed the upper and lower glass substrates, (B) is the state which attached the upper and lower glass substrates. It is explanatory drawing which shows the further another example of the cell for electric field application. It is explanatory drawing which shows the plastic molded product obtained in Example 10. FIG. It is explanatory drawing which shows the manufacturing process of the plastic molded product when the liquid mixture is filled into the application cell for electric fields in layers by film forming. It is explanatory drawing which shows the manufacture process of the plastic molded product of the other example which filled the application liquid for electric fields with the liquid mixture in layer form by film forming. It is explanatory drawing which shows the manufacturing process of the plastic molded product when forming the liquid which comprises a liquid mixture only on one electrode. It is explanatory drawing which shows the manufacture process of the plastic molded product of the other example which formed into a film the liquid which comprises a liquid mixture only on one electrode. It is explanatory drawing which shows the manufacture process of the plastic molded product when the droplet of a high dielectric constant liquid is formed on an electrode surface, and the liquid mixture is filled with the application cell for electric fields. It is an embodiment in which droplets of a high dielectric constant liquid are formed on the electrode surface and the mixed solution is filled in the electric field application cell, and (A) shows a state in which the droplets are formed only on one electrode surface, (B) is an explanatory view showing a state where droplets are formed on both electrode surfaces, and (C) is an explanatory view showing a state where an intermediate layer is interposed between the electrodes and the droplets. In the step of forming droplets of a high dielectric constant liquid on the electrode surface with the surface treatment agent, (A) shows a state where a photoresist is formed on the electrode, and (B) shows a square photoresist in plan view by photolithography. (C) is the state which applied the surface treating agent, (D) is explanatory drawing which shows the state which removed the photoresist and formed the opening. It is explanatory drawing which shows the manufacturing process of the plastic molded product performed by forming the droplet of a high dielectric constant liquid on an electrode surface with a surface treating agent. It is explanatory drawing which shows the manufacturing process of the plastic molded product using photolithography. It is explanatory drawing which shows the manufacturing process of the plastic molded product using a LIGA process. It is explanatory drawing which shows the manufacturing process of the plastic molded product using rapid prototyping.

Explanation of symbols

1 Electric field application cell (Plastic molded product manufacturing equipment)
2 Glass substrate (substrate)
3 Electrode 4 Electrode 5 Power supply (electric field applying means)
7 Dispersion 11 Bridge structure 14 Bridge (plastic molding)
15 Plastic molded product 18 Electric field application cell (Plastic molded product manufacturing equipment)
19 Glass substrate (substrate)
20 Glass substrate (substrate)
21 Power supply (electric field applying means)
22 Electrode 23 Electrode 29 Electric field application cell (Plastic molded product manufacturing equipment)
30 Glass substrate (substrate)
31 Electrode 32 Electrode 36 Power supply (electric field applying means)
37 Bridge structure 41 Plastic molded article 42 Electrode 43 High dielectric constant liquid layer 44 Electrode 45 Low dielectric constant liquid layer 46 Power supply (electric field applying means)
48 Bridge structure 49 Electrode 50 Liquid droplet of high dielectric constant 51 Discharge machine 52 Layer of low dielectric constant liquid 53 Electrode 54 Power supply (electric field applying means)
56 Bridge structure 60 Electrode 62 Surface treatment agent 63 Opening 64 Liquid droplet of high dielectric constant liquid 65 Discharge machine 66 Electrode

Claims (17)

In a mixed liquid supplying step of filling a mixed liquid composed of at least two kinds of liquids that are insoluble and have different dielectric constants into an electric field applying cell in which electrodes are arranged to face each other, the first cell constituting the electric field applying cell A step of forming a first liquid of at least two kinds of liquids constituting the liquid mixture in a layered manner on the electrode surface of the liquid crystal, and the mixing on the second electrode surface constituting the electric field application cell. A step of forming a second liquid of at least two liquids constituting the liquid in a layer form, the first electrode surface on which the first liquid is formed, and the second liquid formed. A step of producing an electric field application cell in which the mixed liquid is formed in a layer by the step of bonding the second electrode surface ;
An electric field applying step of collecting a liquid having a high dielectric constant so as to extend in the electric field direction by applying an electric field between the electrodes to form a bridge structure that connects the electrodes. ,
At least one of the liquids constituting the mixed liquid is an uncured curable resin, and the curable resin is cured after the bridge structure is formed. In a mixed liquid supplying step of filling a mixed liquid composed of at least two kinds of liquids that are insoluble and have different dielectric constants into an electric field applying cell in which electrodes are arranged to face each other, the first cell constituting the electric field applying cell A step of forming, as a droplet, a high dielectric constant liquid having the highest dielectric constant among at least two kinds of liquids constituting the mixed liquid on the electrode surface, and at least two kinds constituting the mixed liquid thereon Of the electric field application cell filled with the mixed solution by the step of forming a liquid other than the high dielectric constant liquid in a layered manner and the step of bonding the second electrode surface constituting the electric field application cell A step of producing
An electric field applying step of collecting a liquid having a high dielectric constant so as to extend in the electric field direction by applying an electric field between the electrodes to form a bridge structure that connects the electrodes. ,
At least one of the liquids constituting the mixed liquid is an uncured curable resin, and the curable resin is cured after the bridge structure is formed. In a mixed liquid supplying step of filling a mixed liquid composed of at least two kinds of liquids that are insoluble and have different dielectric constants into an electric field applying cell in which electrodes are arranged to face each other, the first cell constituting the electric field applying cell A step of forming a high dielectric constant liquid having the highest dielectric constant among at least two kinds of liquids constituting the mixed liquid as droplets on the electrode surface of the liquid crystal, and a second electrode constituting the electric field applying cell. On the surface, a step of forming a liquid other than the high-dielectric-constant liquid out of at least two kinds of liquids constituting the mixed liquid, the first electrode surface on which the droplets are formed, and the layer A step of producing an electric field application cell filled with the mixed liquid by a step of bonding the formed second electrode surface;
An electric field applying step of collecting a liquid having a high dielectric constant so as to extend in the electric field direction by applying an electric field between the electrodes to form a bridge structure that connects the electrodes. ,
At least one of the liquids constituting the mixed liquid is an uncured curable resin, and the curable resin is cured after the bridge structure is formed. 4. The droplet is formed by depositing the high dielectric constant liquid on the electrode surface by depositing the substance that repels the high dielectric constant liquid in a pattern. Manufacturing method for plastic moldings. The method for producing a plastic molded product according to any one of claims 1 to 4 , wherein the curable resin is an active energy ray curable resin that is cured by irradiation with an active energy ray. 6. The method for producing a plastic molded product according to claim 5 , wherein the active energy ray curable resin is an ultraviolet curable resin that is cured by irradiation with ultraviolet rays. The method for producing a plastic molded product according to any one of claims 1 to 4 , wherein the curable resin is a thermosetting resin that is cured by heating. The method for producing a plastic molded product according to any one of claims 1 to 7 , wherein the mixed liquid is composed of two types of liquids that are insoluble and have different dielectric constants. Of the two types of liquids constituting the mixed liquid, the liquid having a high dielectric constant is an uncured curable resin, and the liquid other than the liquid having the high dielectric constant is removed after the curable resin is cured. The method for producing a plastic molded product according to claim 8 . The mixed solution is the dielectric constant of high curing resin liquid other than the liquid uncured constituting, according to claim 8, characterized in that the removal of the high dielectric constant liquid after curing of the curable resin Manufacturing method for plastic moldings. A liquid having a high dielectric constant constituting the liquid mixture is a first uncured curable resin, and a liquid other than the liquid having a high dielectric constant is different from the first uncured curable resin. 9. The method for producing a plastic molded article according to claim 8 , wherein the second curable resin is cured after the first curable resin is cured. . The liquid with a high dielectric constant is an uncured curable resin, and the liquid other than the liquid with a high dielectric constant is a melt of a hot-melt material that melts by heating, and after the curable resin is cured, the liquid The method for producing a plastic molded article according to claim 8 , wherein the melt of the hot-melt material is cured. The liquid having a high dielectric constant is an uncured curable resin, and the liquid other than the liquid having a high dielectric constant is a melt of a hot-melt material that melts by heating, and the melt of the hot-melt material is cured. The method for producing a plastic molded article according to claim 8 , wherein the curable resin is cured after a while. The liquid other than the liquid having a high dielectric constant is an uncured curable resin, and the liquid having a high dielectric constant is a melt of a hot-melt material that melts by heating, and after the curable resin is cured, the liquid The method for producing a plastic molded article according to claim 8 , wherein the melt of the hot-melt material is cured. The liquid other than the liquid having a high dielectric constant is an uncured curable resin, and the liquid having a high dielectric constant is a melt of a hot melt material that melts by heating, and the melt of the hot melt material is cured. The method for producing a plastic molded article according to claim 8 , wherein the curable resin is cured after a while. 16. The method for producing a plastic molded product according to claim 1, wherein the electric field applied between the electrodes is an alternating electric field. The method of manufacturing a plastic molded product according to any one of claims 1 to 15 , wherein the electric field applied between the electrodes is a direct current electric field.

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