JPH06345881A - Water-repellent material and its production - Google Patents

Abstract

PURPOSE:To obtain a material high in water repellency by providing a resin layer incorporated with fluororesin powder followed by abrading the surface of the resin layer to expose the fluororesin powder on the surface. CONSTITUTION:This water-repellent material having 1-5 (pref. 2-4.5) mum surface roughness can be obtained by providing a resin layer incorporated with fluororesin powder (e.g. polytetrafluoroethylene resin) followed by abrading the surface of the resin layer. The resin layer can be obtained, for example, by kneading a base resin such as vinyl chloride resin or polyolefinic resin with fluororesin powder followed by molding processing. It is preferable that the base resin be incorporated with the fluororesin powder of 5-10mum particle diameter so as to reach 10-30 % in the surface density.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a material exhibiting water repellency.

[0002]

BACKGROUND OF THE INVENTION From the viewpoint of preventing the attachment of various organisms and preventing contamination, it has been required to make the surface of the material water repellent. By the way, although fluorine-based resins and silicon-based resins are known as water-repellent materials,
There is a demand for the development of technology that exhibits even greater water repellency.

In addition, a normal resin, not a special resin such as a fluorine-based resin or a silicon-based resin, is used.
For example, it is required to develop a technique of exhibiting water repellency even in a resin such as vinyl chloride resin, styrene resin, or olefin resin.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a material exhibiting water repellency. The object of the present invention is to have a fluororesin powder intervening in a resin body and having a surface roughness of about 1 to 5 μm.
It is achieved by a water repellent material characterized by being m. Further, a water-repellent material characterized by comprising a resin layer forming step of forming a resin layer in which a fluorine-based resin powder is interposed, and a polishing step of polishing the resin layer surface after the resin layer forming step. This is achieved by the manufacturing method.

Further, a resin layer forming step of forming a resin layer in which fluororesin powder is interposed, a heat treatment step of heat treating the resin layer after the resin layer forming step, and a resin layer after the resin layer forming step. And a polishing step of polishing the surface. Any resin may be used as a base (matrix) constituting the water-repellent material in the present invention.
For example, various vinyl chloride resins such as hard vinyl chloride resin, semi-rigid vinyl chloride resin, and soft vinyl chloride resin, vinyl chloride copolymer such as PVC-EVA, polyethylene and polypropylene. Various resins such as a polyolefin resin, a polystyrene resin, a polyester resin, and a polyamide resin can be used. That is, as long as a resin different from the below-mentioned fluorine-based resin powder is used, any resin can be applied.

As the fluorine-based resin which constitutes the fluorine-based resin powder used in the present invention, for example, resins such as tetrafluoride polyethylene resin, low polymerization degree tetrafluoride polyethylene and graphite fluoride are used. Of course, it is not limited to these. To form the resin layer in which the above-mentioned fluororesin powder is interposed, for example, a resin to be a base (matrix), the fluororesin powder, and if necessary, a lubricant, a stabilizer, etc. are added and kneaded. ,
It is obtained by molding.

It can also be obtained by applying and drying a coating material obtained by adding a base (matrix) resin and a fluororesin powder to a desired solvent. Various other methods are conceivable, but the detailed description thereof will be omitted because the method does not matter. The fluorine-based resin powder used in the present invention preferably has a particle size of about 1 to 10 μm, more preferably about 5 to 10 μm.

The ratio of the fluororesin powder to the base (matrix) resin is such that the surface density of the fluororesin powder in the surface layer (for example, a layer up to a depth of about the particle size of the fluororesin powder). , About 5-40%, preferably about 1
It is preferably about 0 to 30%. That is, if the amount of the fluororesin powder is too small, the degree of improvement in water repellency is low. Even when the amount of the fluorine-based resin powder is small, the water repellency is higher than that in the case of no addition.

After the resin body having the fluororesin powder interposed is obtained as described above, the surface roughness of the resin body is about 1 to 5 μm, preferably about 2 to 4.5 μm. So that the polishing is performed. The polishing in the present invention means a surface roughness of about 1 to 5 μm, preferably about 2 to 4.5 μm.
This means that the surface is roughened in advance when it is smoother than this, and it means that the surface is polished when the surface is rough.

The surface roughness is about 1 to 5 μm, preferably about 2
The polishing is performed so that the thickness is up to 4.5 μm, and the fluororesin powder is exposed on the surface, and then heat treatment is performed. The heat treatment may be performed at a temperature between the melting point and the softening point, and is performed at about 110 to 190 ° C., for example. Hereinafter, the present invention will be specifically described with reference to examples.

[0011]

【Example】

[Example 1] 100 parts by weight of hard vinyl chloride resin, fluororesin powder (Separal lube (Ip) manufactured by Central Glass Co., Ltd., average molecular weight 11500, average particle size 10μ)
m) A composition consisting of 5 to 50 parts by weight, 1 part by weight of stearic acid, 5 parts by weight of lead monoxide, and 10 parts by weight of calcium stearate was sufficiently stirred and mixed, and then kneaded at 160 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature and then formed into a sheet using a hot press, and this was then ground with sandpaper having a polishing grain size of # 120 to # 320, and the surface of the sample was polished. Center line average roughness Ra of about 2 to 4.5 μ
It was about m. And after this 130-190 ℃
It heat-processed at the temperature of. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 1 below.

Table 1 (polishing with a polishing grain size of # 120) Surface treatment temperature PVC Ip 130 ° C. 150 ° C. 170 ° C. 190 ° C. 100 10 125 ° 135 ° 160 ° 140 ° 100 20> 165 °> 165 °> 165 °> 165 ° 100 30> 165 °> 165 °> 165 °> 165 ° 100 50> 165 °> 165 °> 165 °> 165 ° According to this, the fluorine-based resin powder is a hard vinyl chloride. If it is dispersed in the resin and its surface has an appropriate roughness, the hydrophilic contact angle is remarkably large.

The hydrophilic contact angle of the vinyl chloride resin used in this example without the interposition of fluorine resin powder is about 8
It is 2 °, and it can be seen that the thing of this example shows remarkably water repellency. [Example 2] 100 parts by weight of a soft vinyl chloride resin, a fluororesin powder (Separal lube (Ip) manufactured by Central Glass Co., Ltd., an average molecular weight of 11,500, an average particle size of 10 µm)
m) A composition comprising 5 to 50 parts by weight, 1 part by weight of stearic acid, 10 parts by weight of calcium stearate, and 30 parts by weight of calcium carbonate was thoroughly mixed by stirring, and then kneaded at 160 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature, then formed into a sheet using a hot press, and then this was ground with sandpaper having a polishing grain size of # 120 to # 320 to obtain a surface of the sample. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 130 to 190 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., and the results are shown in Tables 2 and 3 below.

Table 2 (polishing with a polishing grain size of # 120) Surface treatment temperature PVC Ip 130 ° C. 150 ° C. 170 ° C. 190 ° C. 100 10 155 ° 160 ° 150 ° 150 ° 100 20 160 ° 160 °> 165 ° 160 ° 100 30> 165 °> 165 °> 165 ° 160 ° 100 50> 165 °> 165 °> 165 ° 160 ° Table-3 (heat treatment temperature 150 ° C) Polishing Grain degree PVC Ip # 120 # 150 # 180 # 240 # 320 100 100 160 ° 145 ° 140 °> 140 °> 145 ° 100 20 160 ° 160 ° 160 ° 145 ° 150 ° 100 30> 165 ° 165 ° 165 ° 160 ° 160 ° 100 50> 165 °> 165 °> 165 °> 165 °> 165 ° According to this, the fluororesin powder is a soft vinyl chloride resin. They are dispersed in, as long as the surface of the appropriate roughness, hydrophilicity contact angle is significantly large.

The hydrophilic contact angle of the vinyl chloride resin used in this embodiment without the interposition of fluorine resin powder is about 8
It is 2 °, and it can be seen that the thing of this example shows remarkably water repellency. [Example 3] 100 parts by weight of semi-rigid vinyl chloride resin,
Fluorine-based resin powder (Cefural lube (Ip) manufactured by Central Glass Co., Ltd., average molecular weight 11500, average particle size 10
μm) 5 to 50 parts by weight, stearic acid 1 part by weight, lead monoxide 5 parts by weight, calcium stearate 3 parts by weight, calcium carbonate 30 parts by weight, dioctyl phthalate 10 to 30.
The composition, consisting of 1 part by weight, is thoroughly mixed with stirring, after which 16
Kneading was carried out at 0 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature and then formed into a sheet using a hot press, and this was then ground with sandpaper having a polishing grain size of # 120 to # 320, and the surface of the sample was polished. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 130 to 190 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 4 and 5 below.

Table 4 (polishing with a grain size of # 120) Surface treatment temperature PVC Ip DOP 130 ° C. 150 ° C. 170 ° C. 190 ° C. 100 30 10 165 ° 165 ° 165 ° 160 ° 100 30 30 165 ° 165 ° 165 ° 160 ° Table-5 (heat treatment temperature 170 ° C) Polishing grain degree PVC Ip DOP # 120 # 150 # 180 # 240 # 320 # 320 100 30 10 165 ° 165 ° 150 ° 140 ° 130 ° 100 30 30 30 165 ° 165 ° 150 ° 150 ° 140 ° According to this, if the fluororesin powder is dispersed in the semi-hard vinyl chloride resin and the surface has an appropriate roughness, the hydrophilic contact angle is It is significantly larger.

The hydrophilic contact angle of the vinyl chloride resin used in this example without the interposition of fluorine resin powder is about 8
It is 2 °, and it can be seen that the thing of this example shows remarkably water repellency. [Example 4] 100 parts by weight of vinyl chloride-ethylene vinyl acetate copolymer resin, fluororesin powder (Separal lube (Ip) manufactured by Central Glass Co., Ltd., average molecular weight 115)
00, average particle size 10 μm) 5 to 50 parts by weight, stearic acid 1 part by weight, lead monoxide 5 parts by weight, calcium stearate 3 parts by weight, calcium carbonate 30 parts by weight, and dioctyl phthalate 0 to 10 parts by weight. After thoroughly stirring and mixing, the mixture was kneaded at 160 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature and then formed into a sheet using a hot press, which was then ground with sandpaper having a polishing grain size of # 120 to # 320, and the surface of the sample was polished. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 130 to 190 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., and the results are shown in Table 6 and Table 7 below.

Table 6 (polishing with a grain size of # 120) Surface treatment temperature PVC Ip DOP 130 ° C. 150 ° C. 170 ° C. 190 ° C. 100 30 0 165 ° 165 ° 165 ° 160 ° 100 30 10 165 ° 165 ° 165 ° 160 ° Table-7 (heat treatment temperature 170 ° C) Polishing grain size PVC Ip DOP # 120 # 150 # 180 # 240 # 320 # 320 100 165 ° 155 ° 150 ° 140 ° 140 ° 100 30 10 165 ° 165 ° 160 ° 145 ° 145 ° According to this, if the fluorine-based resin powder is dispersed in the vinyl chloride-based copolymer resin and the surface has an appropriate roughness, the hydrophilic contact angle is remarkably high. It is getting bigger.

The hydrophilic contact angle of the vinyl chloride-based copolymer resin used in this example without the interposition of the fluorine-based resin powder was about 97 °, and this example shows remarkably water repellency. It turns out to be a thing. Example 5 100 parts by weight of polyethylene, fluororesin powder (Separal Lube (I, manufactured by Central Glass Co., Ltd.)
p), average molecular weight 11500, average particle size 10 μm) 5
A composition consisting of 50 parts by weight and 5 parts by weight of calcium stearate was thoroughly mixed by stirring, and then kneaded at 160 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature, then formed into a sheet using a hot press, and thereafter, this was ground with sandpaper having a polishing grain size of # 120 to # 320, and the surface of the sample was polished. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 110 to 170 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd., and the results are shown in Tables 8 and 9 below.

Table 6 (polishing with a polishing grain size of # 120) Surface treatment temperature PE Ip 110 ° C. 130 ° C. 140 ° C. 150 ° C. 100 30 145 ° 150 ° 142 ° 123 ° Table-7 (heat treatment temperature 130 ℃) Polishing degree PE Ip # 120 # 150 # 180 # 240 # 320 100 30 150 ° 130 ° 123 ° 97 ° 117 ° According to this, the fluorine-based resin powder is dispersed in polyethylene, and its surface If has a suitable roughness, the hydrophilic contact angle is remarkably large.

The hydrophilic contact angle of polyethylene used in this example without the interposition of fluorine resin powder was about 82.
It can be seen that the water-repellent property of the present example is remarkably water-repellent. [Example 6] 100 parts by weight of polypropylene, fluororesin powder (Sefraral Lube (I, manufactured by Central Glass Co., Ltd.)
p), average molecular weight 11500, average particle size 10 μm) 5
A composition consisting of 50 parts by weight and 5 parts by weight of calcium stearate was thoroughly mixed by stirring, and then kneaded at 170 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature and then formed into a sheet by using a hot press, which was then ground with sandpaper having a polishing particle size of # 120 to # 320 to obtain a surface of the sample. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 110 to 190 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 10 below.

Table-10 (polishing with a polishing grain size of # 120) Surface treatment temperature PP Ip 130 ° C. 150 ° C. 170 ° C. 180 ° C. 100 10 −145 ° − − 100 20 −150 ° − − 100 30 30 155 ° 160 ° 165 ° 160 ° 100 50 -160 ° --- According to this, if the fluororesin powder is dispersed in polypropylene and its surface has an appropriate roughness,
The hydrophilic contact angle is extremely large.

The hydrophilic contact angle of the polypropylene used in this example without the interposition of the fluororesin powder was about 7.
It is 2 °, and it can be seen that the thing of this example shows remarkably water repellency. [Example 7] 100 parts by weight of polystyrene, fluororesin powder (Separal Lube (I, manufactured by Central Glass Co., Ltd.)
p), average molecular weight 11500, average particle size 10 μm) 5
A composition consisting of 50 parts by weight and 5 parts by weight of stearic acid was thoroughly stirred and mixed, and then kneaded at 190 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature, then formed into a sheet using a hot press, and then this was ground with sandpaper having a polishing particle size of # 120 to # 320 to obtain a surface of the sample. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 110 to 190 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 11 below.

Table-11 (polishing with a grain size of # 120) Surface treatment temperature PS Ip 115 ° C 130 ° C 150 ° C 170 ° C 100 30 160 ° 165 ° 150 ° 130 ° If the resin powder is dispersed in polystyrene and the surface thereof has an appropriate roughness, the hydrophilic contact angle is remarkably large.

The hydrophilic contact angle of polystyrene used in this example without the interposition of fluorine resin powder was about 73.
It can be seen that the water-repellent property of the present example is remarkably water-repellent. Example 8 30 parts by weight of high impact polystyrene, 70 parts by weight of polystyrene, fluororesin powder (Separal lube (Ip) manufactured by Central Glass Co., Ltd., average molecular weight 115)
00, average particle size 10 μm) 5 to 50 parts by weight, and 5 parts by weight of stearic acid were thoroughly mixed by stirring, and then kneaded at 190 ° C. for 5 minutes.

The sample thus obtained was allowed to stand at room temperature, then formed into a sheet using a hot press, and then this was polished with sandpaper having a grain size of # 120 to # 320 to obtain a surface of the sample. Center line average roughness Ra of about 2 to 4.5 μ
m. Then, after this, heat treatment was performed at a temperature of 110 to 170 ° C. The hydrophilic contact angle of the sheet obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 11 below.

Table-11 (polishing with a grain size of # 120) Surface treatment temperature HIPS + PS Ip 115 ° C 130 ° C 150 ° C 170 ° C 100 30 160 ° 160 ° 150 ° 125 ° According to this If the resin powder is dispersed in polystyrene and the surface thereof has an appropriate roughness, the hydrophilic contact angle is remarkably large.

It should be noted that the hydrophilic contact angle of the blended resin of polystyrene and high-impact polystyrene used in this example without the interposition of the fluorine-based resin powder is about 62 °, and that of this example is remarkably high. It can be seen that it exhibits water repellency. [Example 9] With respect to resins such as polyethylene terephthalate, polyvinylidene fluoride, and ethylene-vinyl acetate copolymer, if the fluororesin powder is dispersed and the surface has an appropriate roughness, the hydrophilic contact angle Was remarkably increased, and it was confirmed that the water repellency was exhibited.

[Example 10] Soft vinyl chloride resin 1
00 parts by weight, fluororesin powder (Central Glass Co., Ltd.
Manufactured by Cefraral Lube (Ip), average molecular weight 11500,
Average particle size 10 μm) 30 parts by weight, tetrahydrofuran 1
A composition comprising 70 parts by weight was thoroughly mixed with stirring, the coating material thus obtained was cast on a glass plate, and dried to form a film.

This film has a polishing grain size of # 120 to # 3.
Polishing was performed with 20 sandpapers so that the center line average roughness Ra of the surface was about 2 to 4.5 μm. Then, after this, heat treatment was performed at a temperature of 130 to 190 ° C. The hydrophilic contact angle of the film obtained as described above was measured by a surface contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 12 below.

Table-12 (polishing with a polishing grain size of # 120) Surface treatment temperature 130 ° C. 150 ° C. 170 ° C. 160 ° 165 ° 160 ° According to this, even in the case where the coating means is used, the binder is used. It can be seen that when the fluorine-based resin powder is dispersed in the resin and the surface thereof has an appropriate roughness, the hydrophilic contact angle is remarkably large and the film exhibits water repellency.

[0039]

[Effect] A material having excellent water repellency can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Ouchi 4-6-14 Shibaura, Minato-ku, Tokyo TEPCO Environmental Engineering Co., Ltd. (72) Inventor Akio Tokuumi 1-14 Namamugi, Tsurumi-ku, Yokohama-shi, Kanagawa −50− 305

Claims (3)

[Claims] 1. A water-repellent material, characterized in that a fluororesin powder is interposed in a resin body and the surface roughness is about 1 to 5 μm. 2. A resin layer forming step of forming a resin layer having fluororesin powder intervening, and a polishing step of polishing the surface of the resin layer after the resin layer forming step. A method for producing an aqueous material. 3. A resin layer forming step of forming a resin layer having a fluororesin powder interposed, a heat treatment step of heat treating the resin layer after the resin layer forming step, and a resin layer after the resin layer forming step. And a polishing step of polishing the surface.