JP5177652B2 - Highly water-repellent or super-water-repellent material and method for producing the same - Google Patents

Description

  The present invention relates to a highly water repellent or super water repellent material having a contact angle with water of 120 to 170 ° and a method for producing the same.

  Conventionally, as a method for producing a water-repellent surface, (1) reducing the surface energy of the material and (2) forming an uneven structure on the surface of the material are known. As a method of (1), for example, a method of coating a fluorine compound on the surface of a base material made of a thermoplastic resin is well known, but the contact angle with water on the surface made of a fluorine compound is maximum. It is about 110 °. Therefore, in order to produce a surface having higher water repellency or super water repellency than this surface, it is necessary to form the uneven structure (2).

There are various ways to form a water-repellent surface by forming a fine uneven pattern on the surface of a substrate such as metal or glass by an etching method, sandblasting method, photolithography method, etc., and covering with a fluorine compound or a fluororesin. Proposed. (For example, see Patent Documents 1 to 3)
JP-A-4-288349 JP 10-2449977 WO00 / 50232

However, the techniques described in these patent documents cover a water-repellent film after forming a fine concavo-convex pattern on the substrate surface by combining complicated processes such as masking, chemical pretreatment and etching. Therefore, the manufacturing process is complicated and the manufacturing cost is increased. In addition, it is extremely difficult to form a concavo-convex pattern having a large area and uniform size on the surface of the substrate, and there is a problem that the water repellency of the surface obtained is uneven.
On the other hand, known fluorine compounds or fluorine resins as water repellent materials are expensive and difficult to process.
Accordingly, there has been a demand for a technique for producing a highly water-repellent or super-water-repellent material having a uniform water repellency in a simple process, using an inexpensive organic material, efficiently and at low cost.

  Therefore, the present invention solves these problems of the prior art, and is a highly water-repellent or super-water-repellent material that is uniformly uniform and has a water repellency higher than that of a fluororesin based on an inexpensive organic material, and the high water repellency. Alternatively, an object is to provide a method for producing a super water-repellent material efficiently and at low cost by a simple process.

As a result of intensive studies, the present inventors have found that a 100-8000 mesh mesh pattern formed by thermal transfer on the surface of a base material made of an organic material having a contact angle with water of the base surface before treatment of 80 ° or more. It has been found that a highly water-repellent or super-water-repellent material having a contact angle with water of 120 to 170 ° can be obtained by providing the present invention, and the present invention has been completed.
That is, the present invention employs the following configurations 1 to 8.
1. Water having a 100 to 8000 mesh mesh pattern formed by thermal transfer on the surface of a base material made of an organic material having a contact angle with water of the base material surface before treatment of 80 ° or more. A highly water repellent or super water repellent material having a contact angle of 120 to 170 °.
2. 2. The highly water-repellent or super-water-repellent material according to 1, wherein the mesh pattern is formed by direct thermal transfer on the surface of a base material made of an organic material.
3. 3. The highly water-repellent or super-water-repellent material having transparency according to 1 or 2, wherein the organic material is a polystyrene resin.
4). The high repellent property according to any one of 1 to 3, wherein the mesh pattern is formed by thermally transferring a wire mesh having a wire diameter of 1 to 100 µm and an opening of 0.1 to 100 µm. Water-based or super water-repellent material.
5. A substrate made of an organic material having a contact angle with water on the surface of the substrate before treatment of 80 ° or more is heated to a softening temperature or more, and a mesh pattern of 100 to 8000 mesh is formed on the surface by thermal transfer. A method for producing a highly water-repellent or super-water-repellent material having a contact angle with water of 120 to 170 °.
6). 6. The method for producing a highly water-repellent or super-water-repellent material having transparency according to 5, wherein the organic material is a polystyrene resin.
7). Thermally transferring a wire mesh having a wire diameter of 1 to 100 μm and an opening of 0.1 to 100 μm to the surface of a base material made of an organic material having a contact angle with water of the base material surface before treatment of 80 ° or more. 5. A method for producing a highly water-repellent or super-water-repellent material as described in 5 or 6 above.
In the present invention, the mesh means the number of meshes in the horizontal direction (one direction) between 1 inch unless otherwise specified.

  According to the present invention, it is possible to produce a highly water-repellent or super-water-repellent material, which is uniformly based on an inexpensive organic material and has a water repellency higher than that of a fluororesin, efficiently and at low cost by a simple process. It becomes. The water repellent material of the present invention has extremely excellent water repellency and oil repellency with a contact angle with water of 120 to 170 °, and also has excellent durability. Therefore, it is useful as a material that constitutes a member that needs to prevent snow accretion, icing, clouding, and the like, such as power transmission lines, traffic signs, and building materials.

In the present invention, a net such as a wire net is used as a template (mold), and the template is thermally transferred onto the surface of a fluororesin substrate heated to a temperature higher than the softening temperature, whereby the surface is 100 to 8000 mesh, preferably 300 to 5000 mesh. A highly water-repellent or super-water-repellent material with a contact angle with water of 120 to 170 ° is produced.
The surface contact angle with water of a thin film made of polytetrafluoroethylene (trade name “Teflon”: registered trademark), which is a kind of fluororesin, is about 108 °. The water repellent material has a contact angle with water of 120 to 170 ° and exhibits a property called high water repellency or super water repellency higher than that of a fluororesin.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the following specific examples do not limit the present invention.
FIG. 1 is a schematic diagram for explaining an example of a method for producing a highly water-repellent or super-water-repellent material of the present invention.
In this method, on a hot plate 1 having a heating means (not shown) such as an electric heater, a base 3 made of an organic material such as a wire mesh 2 and a polystyrene resin as a template is placed. The cold plate 4 is disposed above the space with a space. Next, the base material 3 is heated and softened on the hot plate 1, the hot plate 1 and the cold plate 4 are moved close to each other in the direction of the arrow, and the base material 3 and the wire mesh 2 are heated and pressurized. Then, the mesh pattern of the metal mesh 2 serving as a template is thermally transferred to the surface of the base material 3. When the thermal transfer is completed, the hot plate 1 and the cold plate 4 are separated from each other in the direction opposite to the arrow, and the base material 3 is peeled off from the wire mesh 2 and then ultrasonically washed in water. A formed highly water repellent or super water repellent material is obtained.

  There is no restriction | limiting in particular in the kind of organic raw material which comprises the base material 3, As long as the contact angle with the water of the base-material surface before a process is 80 degrees or more, and usually it is about 80-110 degrees, all are organic materials. Can be used. Preferred organic materials include, for example, polystyrene resins such as polystyrene and polystyrene copolymer resins; polyolefin resins such as polyethylene, polypropylene, and copolymer resins thereof; chlorine vinyl resins such as polyvinyl chloride and polyvinylidene chloride; acrylic resins Resins; Silicone resins such as silicone resins, styrene / silicone copolymer resins, and acrylic / silicone copolymer resins.

Any template can be used as long as it is made of a material that can withstand heat and pressure, but a commercially available wire mesh made of a metal such as iron or stainless steel is usually used.
There is no particular limitation on the weaving method of the mesh pattern of such a wire mesh, and various types such as a plain weave wire mesh (FIG. 2A), a twill weave wire mesh (FIG. 2B), a twill woven wire mesh (FIG. 2C), a plain woven wire mesh, a plurality of twill weaves, etc. Commercial products can be used.

The mesh size of a commercially available wire mesh is normally indicated by “mesh” which represents the number of meshes that pass between 1 inch (about 2.54 cm), but in the present invention, the mesh size is 100 to 8000 mesh, preferably 300. Using a wire mesh of ˜5000 mesh, a mesh pattern of the same size is formed on the surface of the substrate by thermal transfer. As such a wire mesh, it is preferable to use a wire having a wire diameter of 1 to 100 μm and an opening of 0.1 to 100 μm.
When the mesh is coarser than 100 mesh, it is difficult to obtain a target material having high water repellency. On the other hand, when the mesh is finer than 8000 mesh, it is difficult to obtain the wire mesh itself, and thermal transfer In some cases, clogging may occur, and a desired mesh pattern cannot be formed on the surface of the base material made of an organic material.
The number of times of thermal transfer using a wire mesh is not limited to one, but may be two or more. In the case where the thermal transfer is performed a plurality of times, a mesh pattern formed on the surface of the substrate after the thermal transfer a plurality of times using a wire mesh having a coarse mesh can be in a desired range.

  The heating temperature of the substrate is selected at a temperature at which the resin softens according to the type of resin used. For example, it is usually about 60 to 150 ° C. for polystyrene resins. Moreover, although the pressure at the time of pressurization can be selected suitably, it is about 1-100 MPa normally, Preferably it is about 5-50 MPa. The heating / pressurizing time is appropriately selected according to the type and size of the base material or wire mesh, but is usually about 10 to 200 seconds, preferably about 20 to 100 seconds.

FIG. 3 is a schematic view for explaining another example of the method for producing the highly water-repellent or super-water-repellent material of the present invention.
In this method, a base material 13 made of an organic material is placed on a hot plate 11, the base material 13 is heated and softened on the hot plate 11, and a hot press roll 14 having a wire mesh 12 attached to the surface is used as a base. The mesh pattern of the wire mesh 12 is thermally transferred onto the surface of the fluororesin substrate 13 by pressing against the surface of the material 13 and rotating in the direction of the arrow.
In this method, the hot plate 11 is used to heat and soften the base material 13, but a cold plate is used instead of the hot plate 11, and the surface of the base material 13 is heated by an infrared heater (not shown) or the like. May be directly heated and softened. Moreover, a heating means (not shown) may be provided in the hot press roll 14 so that the base material 13 is softened by the heated hot press roll 14. And the shape of the base material 13 is not restricted to what is on a flat plate, It is also possible to form a mesh pattern on the curved surface like the inner surface or outer surface of a tubular body.

FIG. 4 is a schematic view for explaining still another example of the method for producing the highly water repellent or super water repellent material of the present invention.
In this method, a hot press roll 14 in which a long base material 13 is placed on a transport means 15 such as a chain roller and moved in the direction of a dotted arrow while a metal plate 12 is attached to the cold plate 21 and the surface. By heating and pressurizing the base material 13 using, a mesh pattern is thermally transferred to the surface of the base material 13. The surface of the base material 13 is preferably softened in advance by heating means 16 such as an infrared heater installed in front of the hot press roll 14. Moreover, a heating means (not shown) may be provided in the hot press roll 14 so that the base material 13 is softened by the heated hot press roll 14. According to this method, it is possible to continuously thermally transfer the mesh pattern onto the surface of the long and large-sized base material 13.

EXAMPLES Next, the present invention will be further described with reference to examples, but the following specific examples are not intended to limit the present invention.
Example 1
A commercially available stainless steel 300 mesh (representing the number of horizontal lines between 1 inch), a wire diameter of 40 μm in both vertical and horizontal directions, and using a plain woven wire mesh with an opening of 45 μm as a template, according to the method shown in FIG. A mesh pattern is thermally transferred onto the surface of a substrate made of a polystyrene sheet having a thickness of 0.13 mm at a hot plate 1 temperature of 120 ° C., a cold plate 4 temperature of 25 ° C., a pressure of 10 MPa, and a heating / pressurization time of 30 seconds. did.
An image of the surface contact angle with water on the polystyrene sheet surface before thermal transfer is shown in FIG. 5, and an image of the surface contact angle with water on the surface on which the mesh pattern is thermally transferred is shown on the left side of FIG. The contact angle with water on the sheet surface before thermal transfer (indicated by CA (Contact Angle) in the figure) is about 96 °, but the contact angle with water on the surface after thermal transfer is 126-133 °, and the water repellency is Greatly improved.

(Example 2)
In the same manner as in Example 1, a stainless steel 635 mesh twill wire mesh (commercially available) was used as a template, and a base made of a polystyrene sheet having the same thickness as in Example 1 and a thickness of 0.13 mm by the method described in FIG. The mesh pattern was thermally transferred onto the surface of the material at a temperature of 120 ° C. of the hot plate 1, a temperature of 30 ° C. of the cold plate 4, a pressure of 10 MPa, and a heating / pressurization time of 30 seconds.
An image of the surface contact angle with the water on the surface on which the mesh pattern is thermally transferred is shown on the right side of FIG. The contact angle with water on the surface after thermal transfer was 130-135 °, and the water repellency was greatly improved.

  According to the present invention, it is possible to produce a highly water-repellent or super-water-repellent material, which is uniformly based on an inexpensive organic material and has a water repellency higher than that of a fluororesin, efficiently and at low cost by a simple process. It becomes. The water repellent material of the present invention has extremely excellent water repellency and oil repellency with a contact angle with water of 120 to 170 °, and also has excellent durability. Therefore, it is useful as a material that constitutes a member that needs to prevent snow accretion, icing, clouding, and the like, such as power transmission lines, traffic signs, and building materials.

It is a schematic diagram for demonstrating an example of the method of manufacturing the highly water-repellent or super water-repellent material of this invention. It is a figure explaining how to weave a mesh pattern of a wire mesh. It is a schematic diagram for demonstrating the other example of the method of manufacturing the highly water-repellent or super water-repellent material of this invention. It is a schematic diagram for demonstrating the other example of the method of manufacturing the highly water-repellent or super water-repellent material of this invention. It is an image of the surface contact angle with water of the polystyrene sheet surface before thermal transfer used in Example 1. The images of the surface contact angle with water on the surface of the polystyrene sheet on which the mesh pattern was thermally transferred in Examples 1 and 2, the left side are images of Example 1 and the right side are images of Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,11 Hot plate 2,12 Wire net 3,13 Base material 4,21 Cold plate 14 Hot press roll 15 Chain roller 16 Infrared heater

Claims (7)

Water having a 100 to 8000 mesh mesh pattern formed by thermal transfer on the surface of a base material made of an organic material having a contact angle with water of the base material surface before treatment of 80 ° or more. A highly water-repellent or super-water-repellent material for use in a member requiring water repellency , having a contact angle of 120 to 170 °. 2. The high water repellency for use in a member requiring water repellency according to claim 1, wherein the mesh pattern is formed by direct thermal transfer on the surface of a base material made of an organic material. Super water-repellent material. 3. The substrate made of an organic material is a polystyrene resin, and has high water repellency or super water repellency for use in a transparent member according to claim 1 or 2 that requires water repellency. material. The said mesh pattern is formed by thermally transferring a wire mesh having a wire diameter of 1 to 100 µm and an opening of 0.1 to 100 µm, according to any one of claims 1 to 3. High water repellency or super water repellency material for use in members requiring water repellency. A substrate made of an organic material having a contact angle with water on the surface of the substrate before treatment of 80 ° or more is heated to a softening temperature or more, and a mesh pattern of 100 to 8000 mesh is formed on the surface by thermal transfer. A method for producing a highly water-repellent or super-water-repellent material for use in a member requiring water repellency, wherein the contact angle with water is 120 to 170 °. The substrate made of an organic material is a polystyrene-based resin, and is a highly water-repellent or super-water-repellent material for use in a member requiring transparency and water repellency according to claim 5. Production method. Thermally transferring a wire mesh having a wire diameter of 1 to 100 μm and an opening of 0.1 to 100 μm to the surface of a base material made of an organic material having a contact angle with water of the base material surface before treatment of 80 ° or more. The method for producing a highly water-repellent or super-water-repellent material for use in a member requiring water repellency according to claim 5 or 6.

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