JP2018177274A - Plastic molded body having liquid repellency and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid repellent plastic molded body having a liquid repellent surface formed without performing fluorine plasma treatment on a large area portion.SOLUTION: In a liquid repellent plastic molded body 1 having a liquid repellent surface 100, the liquid repellent surface 100 has a normal pillar 10 or a pinning pillar 20 formed by the bonding of columnar bodies in which fluorine atoms are distributed, at least on one part of the surface.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a liquid repellent plastic molding having a surface excellent in liquid repellency and a method for producing the same.

  In general, plastics are used in various applications because they are easy to mold as compared to glass, metal and the like and can be easily molded into various shapes. Among them, the field of packaging containers such as pouch-like containers (pouches) and bottles is a representative field of applications of plastics.

  By the way, when the above-mentioned container contains a viscous fluid, its drainability is required. That is, in the case of using a viscous fluid as the content, it is required that the content be rapidly and finely discharged without adhering and remaining in the container.

In order to enhance the drainage of the viscous fluid, means is adopted to enhance the liquid repellency to the contents of the plastic surface forming the inner surface of the container and to improve the slippage to the contents.
As such a means, a means of forming unevenness on the surface is known.
Further, the means for providing unevenness on the surface is to physically impart liquid repellency by the surface shape. That is, when the liquid flows on the uneven surface, an air pocket is formed in the recess, the contact state between the uneven surface and the liquid is in solid-liquid contact and gas-liquid contact, and the gas (air) is the most hydrophobic substance. It is. For this reason, by appropriately setting the density of the asperities, extremely high liquid repellency is exhibited. However, in such a method, when the liquid repeatedly flows on the uneven surface, the liquid gradually accumulates in the recess and the air pocket is gradually lost, and as a result, the liquid repellency is gradually reduced. Become.

In Patent Document 1, primary irregularities are formed on the surface as a plastic molded body in which the liquid repellency is prevented from decreasing with time when the liquid repellency is expressed by the irregularities, and at least a part of the primary irregularities is formed. The present applicant has proposed a plastic molded body having a fractal hierarchical surface asperity structure in which fine secondary asperities are formed.
In this molded body, since the more minute secondary unevenness is formed in the area of the primary unevenness, the penetration of the liquid into the primary unevenness is effectively suppressed, and the liquid repellency by the primary unevenness is stably maintained. It is
However, even by such means, there is a limit in suppressing the decrease in the liquid drainage property and the liquid falling property. That is, the liquid can not be completely prevented from entering into the secondary asperity, and the liquid repellency by the air pocket formed in the secondary asperity gradually decreases, and thus, gradually falls within the primary asperity. The liquid will intrude, and again, the drop in liquid repellency over time is inevitable.

  In Patent Document 2, again, with respect to a molded body having the above-described fractal uneven surface structure (rough surface) formed by the present applicant, the surface is formed by subjecting such rough surface to fluorine plasma treatment Methods have been proposed for incorporating fluorine atoms into the resin being used.

The above means chemically improve the liquid repellency of the uneven surface by means of distributing fluorine atoms on the surface, whereby the liquid repellency decreases when the liquid repeatedly flows on the uneven surface. Since the surface distribution of fluorine atoms is performed by fluorine plasma treatment, the surface liquid repellency does not decrease due to the peeling of the fluorine atom film from the surface.
However, when the fluorine plasma treatment for distributing the fluorine atoms on the surface is applied to a large area such as a film, the apparatus becomes large-scaled, which causes a problem of an increase in production cost. Yes. Improvement in this respect is desired.
In addition, although the above means is suitable for making the mouth of the container liquid repellent to prevent dripping, etc., a viscous fluid is always in contact with the liquid repellent surface. At times, liquid repellency may not be sufficiently exhibited, and further improvement is required.

Furthermore, Patent Document 3 discloses a nozzle plate of an ink jet head having a reentrant structure, and the nozzle plate having such a structure exhibits excellent liquid repellency and effectively prevents ink stains on the nozzle head. It is described.
However, such a reentrant structure forms a mask material on a predetermined surface portion of a nozzle plate by photolithography, and then forms a recess that forms a reentrant structure by etching using a dry etching apparatus, and then, It is manufactured by the extremely troublesome means of removing the mask material, and it can be applied to the nozzle plate of the ink jet head made of silicon etc., but in the field of packaging material from the viewpoint of cost and productivity. Not applicable Furthermore, Patent Document 3 does not consider at all the liquid-repellent life and the like in a state in which a viscous liquid is always in contact.

Unexamined-Japanese-Patent No. 2015-80929 JP, 2016-88947, A JP 2013-52546 A

Accordingly, an object of the present invention is to provide a liquid repellent plastic molding having a liquid repellent surface formed without performing a fluorine plasma treatment on a large area portion, and a method for producing the same.
Another object of the present invention is to maintain excellent liquid repellency over a long period of time even when a liquid, especially a viscous fluid, is kept in constant contact, and in the field of packaging materials. It is another object of the present invention to provide a liquid repellent plastic molding that can be manufactured by a method applicable to the present invention and a method for manufacturing the same.

According to the present invention, in a liquid repellent plastic molding having a liquid repellent surface,
The liquid repellent plastic molded body is provided, wherein the liquid repellent surface is an uneven surface having a convex portion formed by joining of columnar bodies in which fluorine atoms are distributed on the surface.

In the liquid repellent plastic molding of the present invention,
(1) The surface of the columnar body is a fluorine plasma treated surface,
(2) The protrusion formed by joining the columnar members has a shape having a head with an enlarged diameter, and the reentrant structure is formed by the arrangement of the protrusions,
(3) The plastic molded body has the form of a film,
Is preferred.
In particular, it is desirable to form a liquid repellent plastic molding in the form of a film and use it as a bag-like container.

According to the invention,
Preparing a plastic molded body formed into a predetermined shape and a plastic columnar body having fluorine atoms distributed on the surface;
A surface forming step of forming a liquid repellent surface by bonding a large number of the columns to the surface of the plastic molded body;
There is provided a method of producing a liquid repellent plastic molding, comprising:

In such a manufacturing method,
(1) In the surface forming step, bonding of the columnar body to the surface of the plastic molded body is performed by electrostatic flocking;
Or,
(2) In the surface forming step, bonding the columnar body to the surface of the plastic molded body is performed by spraying the columnar body on the surface of the plastic molded body,
Can be adopted.

Also, in the above manufacturing method,
(3) The columnar body has a form in which at least one side end portion is expanded in diameter, and a liquid repellent structural surface having a reentrant structure is formed by joining the columnar bodies in this form,
(4) The distribution of fluorine atoms on the surface of the columnar body is carried out by fluorine plasma treatment,
(5) The surface of the columnar body is formed of a resin containing a fluorine-containing compound, and bleeding of the fluorine-containing compound results in distribution of fluorine atoms.
Is preferred.

In the liquid repellent plastic molded body of the present invention, the uneven surface is formed by the projections having fluorine atoms distributed on the surface, and the liquid repellency and the projections provided by the air layer present in the depressions of the uneven surface. The liquid repellent property by the fluorine atoms distributed on the surface is combined with the excellent liquid repellent property also called super liquid repellent property, but the most important feature is that the above-mentioned convex part is a plastic molded body The point is that it is provided by bonding on the surface of.
That is, in the present invention, the surface distribution of fluorine atoms can be limited to the convex portion, and for example, the fluorine plasma treatment may be performed only on the small columnar body surface used for forming the convex portion. In other words, even for a plastic molded body having a large area such as a film, the entire surface of the film may not be subjected to the fluorine plasma treatment. Moreover, this liquid repellent plastic molded body can be manufactured continuously without adopting a method such as direct etching of the surface of the molded body. Therefore, the liquid repellent plastic molding of the present invention has the advantages of low production cost and high productivity.

Further, in the present invention, the liquid repellent surface of the reentrant structured surface can be obtained by having the enlarged head portion of the convex portion joined and arranged on the surface of the plastic molded body. In such a case, even when the liquid is always kept in contact with the liquid repellent surface, the liquid repellency can be stably maintained over a long period of time.
That is, in the reentrant structure, since the head is formed in the arranged convex part, the concave part formed between the convex parts has a shape in which the upper part is narrowed. In such a reentrant structure, when the liquid flows on this surface, the liquid is less likely to enter the recess, and the so-called cassie mode stability is maintained, so that the liquid is always kept in contact and held. Even in the case where it has been used, the liquid repellency is stably maintained for an extremely long time.
Therefore, the liquid repellent plastic molding of the present invention is suitably applied to the packaging field (especially container) where the liquid is always kept in contact, for example, viscous fluid such as curry (eg 25 ° C.) When used as a bag-like container containing as a content a viscosity of 250 mPa · s or more, the content can be attached quickly without remaining inside even after half a year to 1 year has passed from the time of manufacture. Can be discharged.

The schematic diagram which shows the contact pattern of the droplet in a rough surface by Cassie-Baxter model and Wenzel model. Schematic which shows the form of the liquid repellant surface currently formed in the liquid repellant plastic molded object of this invention. The figure which shows the example of the form of the columnar body used for the manufacturing method of this invention. The figure for demonstrating the process of the manufacturing method of this invention using electrostatic flocking. The figure for demonstrating the process of the manufacturing method of this invention which utilized the thermal spraying method.

Referring to FIG. 1 for explaining the principle of liquid repellency by the uneven surface, in the Cassie mode in which a droplet is placed on the uneven surface 100, the recess in the uneven surface 100 is an air pocket, Is a complex contact of solid and gas (air). That is, it is known that in such a complex contact, the radius R at the droplet contact interface is small, and the liquid comes in contact with air having the highest hydrophobicity, so that high water repellency is exhibited. That is, the apparent contact angle θ ^* exhibits a value close to 180 degrees.

On the other hand, when the droplet intrudes into the concave portion in the uneven surface 100, the droplet is not a complex contact but a contact with only a solid, which is shown in the Wenzel mode. In such a Wenzel mode, the contact radius R at the droplet contact interface is large, and in this case also, it is known that the apparent contact angle θ ^* is close to 180 degrees and exhibits liquid repellency.

  As described above, it is known that the liquid repellency is improved in either the Wenzel mode or the Cassie mode, but the Cassie mode is stably maintained instead of the Wenzel mode in order to enhance the liquid repellency. It is considered necessary to do (to keep the air pockets in the recess stable). That is, in the Wenzel mode, the interface between the liquid phase and the solid phase is large, and as a result, the physical adsorption force acting on the interface is also large, so the contact angle is large and liquid repelling is performed. Absent. Since the interface is small in the Cassie mode, the energy barrier which the droplet must fall over is low, and it is considered that the droplet falls easily and falls repeatedly over and over again.

  In the present invention, the form of the liquid repellent surface is designed on the premise that the stable holding of the Cassie mode leads to the stabilization of the liquid repellency.

<Form of liquid repellent surface>
With reference to FIGS. 2 (a) to 2 (c) showing the form of the liquid repellent surface, the liquid repellent plastic molding 1 of the present invention has the liquid repellent surface of the form shown by 100, The liquid repellent surface 100 is an uneven surface formed by the arrangement of the projections 10 or 20.
The liquid repellent surface 100 shown in FIG. 2A has an uneven surface formed by a straight cylindrical convex portion 10 (hereinafter referred to as a normal pillar), and such uneven surface has a pillar structure. I call it a face.

On the other hand, the convex portion 20 forming the liquid repellent surface 100 shown in FIGS. 2 (b) and 2 (c) has a head 20a having an enlarged diameter, and such a head A liquid repellent surface 100 is formed by a projection 20 (hereinafter referred to as a pinning pillar) having a 20 a.
The recess 100a formed by the pinning pillar 20 having such a head 20a has a form in which the upper end of the recess 100a is narrower than the bottom, and such a concavo-convex structure surface is a reentrant structure surface be called. In FIG. 2 (b), the reentrant structure is formed by the arrangement of the pinning pillars 20 of the normal form, and the form of the uneven surface is referred to as a single reentrant structure. On the other hand, in FIG. 2C, the head 20a of the pinning pillar 20 is folded back to form a small space 20b at the peripheral edge, and the uneven surface formed by the pinning pillar 20 having such a space 20b The form of is particularly called a double reentrant structure.

In the present invention, the lyophobic surface 100 is formed by the arrangement of the normal pillars 10 or the pinning pillars 20 as described above, but fluorine atoms are distributed on the surface of each of these pillars 10 and 20. The liquid repellent surface 100 is formed by bonding the columnar body to the surface of the plastic molded body 1.
That is, in the liquid repellent surface 100, the air layer present in the recess 100a and the fluorine atoms distributed on the surface exhibit excellent liquid repellency, also called super liquid repellency, but they are joined together. Since the fluorine atoms are distributed only on the surface of the normal pillar 10 or the pinning pillar 20, the manufacturing cost is greatly reduced, and the production efficiency is greatly improved.

  That is, the distribution structure of fluorine atoms as described above may be formed only for the small columns used for forming the pillars 10 and 20 as described above, and the fluorine atoms may be formed over the entire surface area of the liquid repellent surface. There is no need to go over. Therefore, there is no need for a large plasma apparatus for the process of introducing fluorine atoms, which can significantly reduce the manufacturing cost. This is particularly advantageous when forming a liquid repellent surface on the surface of a plastic molded body having a large area such as a film. In addition, since it is possible to mass-produce and stock pillars for forming a pillar having a surface on which fluorine atoms are distributed, production efficiency is also improved.

  The distribution amount of fluorine atoms distributed on the surface of the normal pillar 10 or the pinning pillar 20 is such that the element ratio (F / C) of fluorine atoms to carbon per unit area is 40% or more, particularly 50 to 300%. The above-mentioned stable super-liquid repellency can be secured without impairing the surface strength. The elemental ratio can be calculated by analyzing the elemental composition of the surface using an X-ray photoelectron spectrometer.

Furthermore, in the present invention, particularly in the case where the liquid is always kept in contact with the liquid repellent surface 100, the excellent liquid repellency can be maintained for a long time, as shown in FIGS. 2 (b) and 2 (c). It is preferred to have the shown reentrant structure, and in particular most preferred to have the doublet entrant structure shown in FIG. 2 (c).
That is, the reentrant structure has a configuration in which the upper end of the recess 100a is narrower than the bottom, and the liquid droplet does not easily enter the inside of the recess 100a. For example, the liquid is always kept in contact Also in the case, the Cassie mode described above is stably maintained for a long time, and as a result, the liquid repellency equivalent to the initial one is maintained even after a long time.

In the pillar structure of FIG. 2A, in the state in which the droplet is placed on the uneven surface 100, the pressure Δp is applied due to the weight or disturbance of the droplet, but the droplet for the material constituting the uneven surface 100 In the case of a liquid repellant state in which the contact angle θE of the liquid is larger than 90 ° (θE = 130 ° in FIG. 2A), the meniscus formed by the surface tension of the droplet has a downward convex shape (pinning Effect), the droplet does not infiltrate into the recess 100a.
However, in the case of a lyophilic state in which the contact angle θE of the droplet is 90 ° or less, the meniscus is convex upward, and the droplet penetrates into the recess 100 a.

On the other hand, in the reentrant structures shown in FIGS. 2 (b) and 2 (c), even in the lyophilic state in which the contact angle θE of the droplets is 90 ° or less (in FIG. 3, θE = 20 °), Since the meniscus formed is convex downward (pinning effect), the droplet does not enter the recess 100a.
In particular, in the double reentrant structure of FIG. 2C, a meniscus with a small curvature is formed, and the meniscus does not invert even when a large pressure ΔP (> Δp) is applied, so excellent liquid repellency is maintained for a long time .

In the reentrant structures of FIGS. 2 (b) and 2 (c) adopted in the present invention described above, in order to sufficiently exert the pinning effect and maintain the liquid repellency over a long period, together with the initial liquid repellency, pinning The pitch p of the pillars 20 is about 1 to 500 μm, and the depth d of the recess 100 a is in the range of about 5 to 200 μm. It is preferable that the two-edge width f2 and the second-edge thickness e2 be approximately 1 to 10 μm.
Further, the area ratio 当 た り per unit projected area of the head 20 a of the pinning pillar 20 occupying the uneven surface 100 is preferably in the range of 0.05 to 0.8.

In the present invention, the plastic molded body 1 on which the liquid repellent surface 100 as described above is formed is any plastic as long as it can be molded into a predetermined shape, for example, a thermoplastic resin, a thermosetting resin, a photocurable resin, etc. According to the use of this molded object 1, an appropriate resin may be selected, and a multilayer structure can also be made.
Generally, in the field of packaging materials, polyesters such as polyethylene, polypropylene, olefin resins represented by copolymers of ethylene or propylene and other olefins, polyethylene terephthalate (PET), polyethylene isophthalate, polyethylene naphthalate, etc. It is typical as a resin for formation.
Furthermore, depending on the application, metal foil such as aluminum foil may be adhered and fixed to the back surface of the plastic molded body 1, or only the normal pillar 10 or the pinning pillar 20 may be formed of other resin .

<Production of liquid repellent plastic molding>
The liquid repellent plastic molded article of the present invention having the liquid repellent surface 100 described above is manufactured by a bonding method.

In order to carry out this method, a pillar for pillar formation is prepared together with the plastic molded body 1 described above.
As such a columnar body, the one shown in FIG. 3 is used. This column is shown at 40 in FIG.

For example, the columnar body 40 shown in FIG. 3A is used to form the normal pillar 10, has a straight barrel shape, and is formed by, for example, melt extrusion of a plastic material.
Moreover, the columnar body 40 shown by FIG.3 (b) and (c) is used for formation of the pinning pillar 20 which forms a re-entrant structure.
For example, the columnar body 40 in FIG. 3 (b) is obtained by cutting a plastic short fiber, and the short fiber is cut to have a shape in which both ends 40a are expanded in diameter. One of them corresponds to the head 20 a of the pinning pillar 20.
Moreover, the columnar body 40 of the form shown by FIG.3 (c) is obtained by cut | disconnecting the twisted yarn which is also formed from the plastic fiber. Also in the columnar body 40, the end 40b is expanded in diameter by cutting, and the end 40b corresponds to the head 20a of the pinning pillar 20. The columnar body 40 shown in FIG. 3 (c) is obtained by cutting a twisted yarn, and thus has a form in which the end 40a is folded back. Therefore, in particular, the double reentrant structure of FIG. 2 (c) The invention is preferably applied to the formation of

As a plastic material for forming the above-described columnar body 40, a resin material which is easily fusion-bonded to the surface of the plastic molded body 1 is used, but generally, a nylon material is inexpensive. Although it is preferably used in that it is easy to obtain and readily available, the same resin material as the surface of the plastic molded body 1 may be spun.
In addition, the thickness and length of the columnar body 40 may have a size corresponding to the normal pillar or the pinning pillar 20 described above.

In the present invention, prior to bonding to the surface of the plastic bag 1, the fluorine atoms are distributed on the surface of the columnar body 40 described above.
Such distribution of fluorine atoms can be carried out by means of blending a fluorine-containing compound having bleeding properties into the plastic used for forming the columnar body 40 (bleeding method) or fluorine plasma treatment.

Examples of the fluorine-containing compound used in the bleeding method include a modified olefin resin having a fluorine-containing alkyl group, a fluorine-containing silane coupling agent, a fluorine-containing surfactant and the like. In particular, when an olefin-based resin is used to form the columnar body 40, the above-described modified olefin-based resin is suitable.
As such a fluorine-containing modified olefin resin, for example, a fluoroalkyl group two-chain polymer represented by the following formula is known. (For example, Tokuzou Kawase; Super Water Repellent / Super Oil Repellent Technology, Textile Disappearance Journal, 55 (6), 2014)
In the above formula, n is an integer indicating the number of repeating units,
R f is a perfluorohexyl group (C ₆ F ₁₃ ).

The fluorine plasma treatment can be carried out by a method known per se. For example, CF ₄ gas or SiF ₄ gas is used, the columnar body 40 is disposed between a pair of electrodes, and a high frequency electric field is applied to generate plasma (atomic fluorine) of fluorine atoms, By collision with the surface of the columnar body 40, a fluorine atom can be incorporated into the molecular chain of the resin on the surface of the columnar body. That is, the resin on the surface is vaporized or decomposed, and at the same time, a fluorine atom is incorporated.

In the present invention, fluorine atoms can be selectively distributed on the surface of the columnar body 40, so that fluorine atoms are applied to the surface of the columnar body 40 (that is, the surface of the normal pillar 10 or the pinning pillar 20) by fluorine plasma treatment. It is most preferable in that it can be distributed. That is, since the columnar body 40 is very small in size, in the bleeding method, the compounding of the fluorine compound impairs the formability, or it is necessary to change the forming conditions.
Further, since such fluorine plasma treatment is to treat the surface of the small columnar body 40, it is not necessary to use a large-sized apparatus as in the treatment of the film surface.

The external additive joining of the columnar body 40 to the surface of the plastic molded body 1 can be performed by electrostatic flocking or thermal spraying. These bonding methods are shown in FIG. 4 and FIG.
In addition, in FIG.4 and FIG.5, the thing of the film shape was shown as the plastic molded object 1. As shown in FIG.

Bonding by electrostatic flocking;
Referring to FIG. 5, in this method, a film 1 which is a plastic molded body is wound around a raw fabric roller 51, and in a conveyance path in which the film 1 is wound by a winding roller 53, bonding by electrostatic flocking is To be done.

That is, the application roller 55 is disposed to face the original film roller 51, and the heat seal lacquer is applied to one surface (surface to be a liquid repellent surface) of the film 1 by the application roller 55.
In addition, a pair of electrodes 57 (anode 57a, cathode 57b) and an oven 59 are disposed between the original fabric roller 51 and the take-up roller 53, and the film 1 coated with the heat seal lacquer is a pair of electrodes. After passing through 57 and heated in the oven 59, the take-up roller 53 takes up the structure.

  In the structure as described above, the columnar body 40 for forming the normal pillar 10 or the pinning pillar 20 described above is held on the cathode 57b, and the film 1 has the surface to which the heat seal lacquer is applied. Is moved along the anode 57a so as to be on the cathode side. In this way, when the film 1 passes between the electrodes 57, a DC voltage (usually about 40 kV) is applied by the power supply 61, whereby the columns 40 on the cathode 57b fly along the electric field, and the film 1. Adhere to the heat-sealed lacquer surface. Thus, the film 1 having the columnar bodies 1 adhering to the surface is heated in the oven 59, and the columnar bodies 40 are firmly fixed to the surface of the film 1, whereby the surface of the film 1 is normal. The pillars 10 or the pinning pillars 20 are joined, and the predetermined liquid repellent surface 100 is formed, and is wound around the take-up roller 53, thereby completing the external additive joining process.

Joining by spraying method;
With reference to FIG. 5, in this method, the film 1 which is a plastic molded body is wound around the raw fabric roller 51, and the columnar body 40 described above is taken along the conveyance path for winding the film 1 by the winding roller 53. Spraying is performed.

  That is, the thermal spraying device 71 and the anode 3 are disposed to face each other in this transport path, and one side of the film 1 moves along the anode 73 and between the thermal spraying device 71 and the anode 73 It is configured to

  The thermal spray apparatus 71 heats a metallic nozzle 75 having a cylindrical space with a straight inside, a thermal spray media supply pipe 77 for supplying the thermal spray media straight into the cylindrical space of the nozzle, and the thermal spray medium. The hot air supply pipe 79 of

  That is, in the thermal spraying method, the columnar body 40 described above is used as the thermal spraying medium, and the columnar body 40 is sprayed on the surface of the film 1 by spraying the heated columnar body 40 on the surface of the film 1 passing over the cathode 73. A liquid repellent surface 100 in which normal pillars 10 or pinning pillars 20 are arrayed is formed by bonding.

For example, in the thermal spraying apparatus 71, the columnar body 40 described above is supplied to the thermal spray media supply pipe 71. The hot air supply pipe 77 supplies hot air for heating the columnar body 40 which is the thermal spray media. The temperature of the hot air is set so that the columnar body 40 attached to the surface of the film 1 is melt-bonded to the surface of the film 1, but heated to a temperature at which the form is maintained. Although the specific temperature varies depending on the material of the columnar body 40, in the case of polyethylene, the temperature immediately before the surface of the film 1 is set to be about 400 to 500 ° C.
Incidentally, as shown in FIG. 5, the thermal spray media supply pipe 77 is straight toward the center of the nozzle 75 so that the columnar members 40 are sprayed onto the surface of the film 1 in a state in which the columnar members 40 are directed in a certain direction. Although extended, a plurality of hot air supply pipes 79 are provided so as to surround the thermal spray media supply pipe 77 in order to uniformly heat the columnar body 40.

  As described above, when the columnar body 40 is heated and sprayed with hot air, a voltage (usually about 40 kV) is applied between the anode 73 and the nozzle 75 by the power supply 81. Thereby, the heated columnar body 40 is sprayed perpendicularly to the surface of the film 1 on the anode 73 along the electric field.

  The columnar body 40 thus heated is sprayed onto the surface of the film 1 and bonded to form a predetermined liquid repellent surface 100. In this state, the film 1 is wound around the winding roller 53, and this bonding is performed. The process is complete.

  In addition, in the example of FIG.4 and FIG.5 mentioned above, although the case where the molded object 1 had a form of a film was taken for an example, also when not having a form of a film, conveyance by a roller is performed It is obvious to those skilled in the art that, if not, it is possible to form a liquid repellent surface having a concavo-convex surface structure in which normal pillars 10 or pinning pillars 20 are arrayed by joining columnar bodies 40 in the same manner.

  The liquid repellent plastic molded article of the present invention thus obtained has excellent liquid repellency or slipperiness with respect to various fluids, and is applied to various uses utilizing this. Be done. In particular, in the liquid repellent plastic molded article of the present invention having the reentrant structure shown in FIG. 2 (b) or (c) on the surface, even when the liquid is always kept in contact, as in the initial stage, The liquid repelling property is excellent, and the reentrant structure described above is not damaged even by heat treatment such as retort sterilization, so that it is suitably applied to the packaging field.

For example, those in the form of a film are most suitably used as a bag-like container or tube container in which the contents are stored for a long time by post-processing such as bag making. In particular, even when a viscous paste-like content having a viscosity (25 ° C.) of 250 mPa or more is contained, the excellent liquid repellency allows the content to be discharged promptly without being adhered and remaining in the container. can do.
Typical examples of such paste-like contents are curry, various foods with a thickened body, gel-like substances such as pudding and yogurt, jams, shampoos, conditioners, liquid detergents, toothpaste and the like.
Of course, the present invention can be applied not only to a bag-like container or a tube container but also to a cup-shaped or tray-shaped container.

1: Plastic molded body 10: normal pillar 20: pinning pillar 20a: pinning pillar head 20b: space 40: columnar body 40a: end of enlarged diameter portion of columnar body 51: original fabric roller 53: take-up roller 55: application roller 57: Electrode 59: Oven 71: Thermal spray apparatus 77: Nozzle 77: Thermal spray media supply pipe 79: Hot air supply pipe 100: Liquid repellent surface 100a: Recess

Claims (11)

In a liquid repellent plastic molding having a liquid repellent surface,
The liquid repellent plastic molded body, wherein the liquid repellent surface is an uneven surface having a convex portion formed by joining of columnar bodies in which fluorine atoms are distributed on the surface.   The liquid repellent plastic molding according to claim 1, wherein the surface of the columnar body is a fluorine plasma treated surface.   The repellent according to claim 1 or 2, wherein the convex portion formed by joining the columnar bodies has a shape having an enlarged head, and the reentrant structure is formed by the arrangement of the convex portions. Liquid plastic molding.   The liquid repellent plastic molding according to any one of claims 1 to 3, which has a film form.   A bag-like container formed by bagging the liquid repellent plastic molding according to claim 4. Preparing a plastic molded body formed into a predetermined shape and a plastic columnar body having fluorine atoms distributed on the surface;
A surface forming step of forming a liquid repellent surface by bonding a large number of the columns to the surface of the plastic molded body;
A method of producing a liquid repellent plastic molding, comprising:   The manufacturing method according to claim 6, wherein the bonding of the columnar body to the surface of the plastic molded body is performed by electrostatic flocking in the surface forming step.   7. The manufacturing method according to claim 6, wherein in the surface forming step, bonding of the columnar body to the surface of the plastic molded body is performed by spraying the columnar body on the surface of the plastic molded body.   The column according to any one of claims 6 to 8, wherein the columnar body has a form in which at least one side end portion is expanded in diameter, and bonding of the columnar body in this form forms a liquid repelling structure surface of a reentrant structure. The manufacturing method described in.   The method according to any one of claims 6 to 9, wherein the distribution of fluorine atoms on the surface of the columnar body is performed by fluorine plasma treatment.   The manufacturing method according to any one of claims 6 to 9, wherein the columnar body surface is formed of a resin in which a fluorine-containing compound is blended, and bleeding of the fluorine-containing compound causes distribution of fluorine atoms.