JP2614825B2 - Snow and ice protection paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a snow- and ice-preventing paint composition which covers the surface of a structure in a snow-covered area to prevent snow and ice formation.

[0002]

2. Description of the Related Art Snow and ice generated in cold snow regions cause various damages and obstacles to ordinary life and industrial activities. For example, a power outage accident occurs in a wide area due to disconnection due to snow on electric wires or collapse of a steel tower. In addition, the snow that the high-speed train soars adheres to the pantograph and the lower part of the vehicle, causing operational obstacles. In addition, snowfall accidents from bridge girder, steel tower, building, house, etc., accidents and obstacles due to snow and ice on ships, vehicles, aircraft, telecommunications facilities, road traffic signs, traffic lights, and icing on the inner walls of snow drifts and snow throw outlets There are obstructions and sometimes life-threatening, and prevention of snow and ice is desired from various fields.

[0003] As a method for coating the surface of a structure with a paint as a measure to prevent snow and icing, a composition comprising an organopolysiloxane resin and an alkali metal compound (JP-B-63-62556) has been proposed. I have.

[0004]

When observing the phenomenon of snow and ice in a cryo-icological manner, the adhesion of wet snow to an object depends on the surface tension of water contained in snow, and the adhesion of dry snow to snow and an object. This is because an ice bond is formed between them. That is, the adhesion of snow and ice is due to hydrogen bonding, van der Waals force, and the like formed between water molecules and atoms located on the surface of the object. Therefore, to prevent snow and ice, it is necessary to reduce the bond between water molecules and the surface of the object, and it is essential to increase the contact angle with water, that is, to reduce the solid surface free energy of the object. . Furthermore, since snow and ice prevention materials are used outdoors, the coatings themselves must have weather resistance and strength to maintain their properties.

However, the composition comprising the organopolysiloxane resin and the alkali metal compound has a solid surface free energy of 28.1 (erg / cm 2), which is not a small value. Furthermore, the weather resistance of the organopolysiloxane resin is
The change over time of the contact angle with water is 2 to 2 compared to the fluorine-containing resin system.
It is three times. Further, since the organopolysiloxane resin shows rubber elasticity, the coating film strength is small. In addition, organopolysiloxane resins are more expensive than general synthetic resins.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the prevention of snow and ice in order to solve the above-mentioned problems, and as a result, by combining a specific hydrophobic compound and mixing it with a fluorinated copolymer resin. It has been found that a coating composition for preventing snow and ice having a small solid surface free energy, good weather resistance of the coating film itself and high coating film strength can be obtained.

[0007] The coating composition for preventing snow and ice in the present invention comprises:
Fluorine-containing copolymer resin whose essential components are 40 to 80% by weight of a fluorine-containing copolymer resin composed of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, and 60 to 20% by weight of an acrylic resin containing methyl methacrylate And one kind selected from a nonionic surfactant, a fluorine surfactant, a low molecular weight ethylene tetrafluoride polymer powder, and a silicon resin powder with respect to 100 parts by weight of the fluorine-containing copolymer resin. Alternatively, it is characterized in that 0.1 to 200 parts by weight of two or more hydrophobic compounds are mixed.

The proportion of the fluorocopolymer resin in the fluorocopolymer resin is 40 to 80% by weight, and the proportion of the acrylic resin is 60% by weight.
~ 20% by weight. If the proportion of the fluorocopolymer resin is more than 80% by weight, the adhesion and the strength of the coating film are reduced,
On the other hand, if it is less than 40% by weight,
The stain removal resistance is impaired, and in either case, it is not preferable. When the proportion of the acrylic resin is more than 60% by weight, the weather resistance and stain removal resistance of the coating film are impaired. On the other hand, when the proportion is less than 20% by weight, the adhesion and the strength of the coating film decrease. In any case, it is not preferable.

The hydrophobic compound includes a nonionic surfactant,
Fluorinated surfactant, low molecular weight ethylene tetrafluoride polymer powder, one or more selected from silicone resin powder, the ratio of which is 0.1 to 100 parts by weight of the fluorine-containing copolymer resin 200200 parts by weight, preferably 0.5-100 parts by weight. When the proportion is more than 200 parts by weight, the coating composition becomes non-uniform, while when the proportion is less than 0.1 part by weight, the effect of hydrophobicity is not exhibited, and any case is not preferable.

The proportion of vinylidene fluoride as a monomer component of the fluorocopolymer resin is preferably from 60 to 75% by weight. When the proportion is more than 75% by weight, the solubility in the organic solvent is reduced. On the other hand, when the proportion is less than 60% by weight, the coating composition is reduced in both cases due to the reduced compatibility with the acrylic resin. It becomes uneven. The proportion of tetrafluoroethylene is preferably between 20 and 40% by weight. If this proportion is more than 40% by weight, the compatibility with the acrylic resin is reduced, while if it is less than 20% by weight, the composition of the coating film is not uniform, which is not preferable. The proportion of hexafluoropropylene is preferably at most 20% by weight. If the proportion is more than 20% by weight, a rubber-like property appears and the coating film is too soft, which is not preferable.

The proportion of methyl methacrylate as a monomer component of the acrylic resin is preferably at least 90% by weight. If this proportion is less than 90% by weight, the compatibility with the fluorocopolymer resin is undesirably reduced.

Examples of the nonionic surfactant of a hydrophobic compound include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, and sorbitan fatty acid ester. Examples of the fluorinated surfactant include perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ammonium salt and the like. Low molecular weight ethylene tetrafluoride polymer has an average molecular weight of 1,500 to 20,000 and an average particle size of 0.1 to 20 μm
Is a perfluorinated compound. The silicon resin powder has an average particle size of 0.1 to 20 μm.

The organic solvent for dissolving the fluorocopolymer resin and the acrylic resin is a ketone-based, ester-based, or ether-based organic solvent. For example, methyl n-propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, ethyl n-butyl ketone, cyclohexanone, n-propyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve, 2-methoxy-2- And propanol cellosolve. And this fluorocopolymer resin and acrylic resin are not aqueous dispersible.

The preparation of the snow / ice protection coating composition of the present invention as a coating composition is carried out by adding the above-mentioned fluorinated copolymer resin, a hydrophobic compound, an organic solvent and, if necessary, additives such as a leveling agent and a coloring agent. It is performed by mixing, and the method can be performed using a ball mill, a roll mill, or the like, which is a general dispersion method.

The paint thus produced can be applied to the surface of steel, aluminum, stainless steel, glass, vinyl chloride resin, acrylic resin, reinforced plastic, etc.
An epoxy-based or urethane-based primer can be used to improve adhesion.

[0016]

The hydrophobic compound according to the present invention has a functional group having a small critical surface energy in its molecular structure. Representative examples thereof include a methyl group and a trifluoromethyl group. Mix them into a fluorocopolymer resin,
By dispersing, they exhibit very low solid surface energy and exhibit high hydrophobicity. As a result, a good snow and ice prevention paint composition can be obtained.

Further, the above-mentioned fluorine-containing copolymer resin exhibits excellent weather resistance and coating film strength. Regarding weather resistance, the change in contact angle with water exposed for 1200 hours by accelerated weathering test (Sunshine Weather Meter manufactured by Suga Test Instruments Co., Ltd.)
It was one-half to one-third of the organopolysiloxane resin. It is a well-known fact that the durability of the color difference and gloss of fluororesin paints due to outdoor exposure is better than other synthetic resin paints. Further, the coating film strength of the fluorocopolymer resin was H to 2H in pencil hardness. From the above points, the fluorinated copolymer resin is superior to the organopolysiloxane resin.

[0018]

The present invention will be specifically described below with reference to examples and comparative examples. Example 1 Fluorine resin copolymer resin 70% by weight and acrylic resin 30
100% by weight of a fluorine-containing copolymer resin composed of 100% by weight of polyoxyethylene alkyl ether (trade name: Emulgen PP15 manufactured by Kao Corporation)
0) 10 parts by weight, 100 parts by weight of cyclohexanone as an organic solvent, 60 parts by weight of butyl acetate, and 40 parts by weight of methyl isobutyl ketone were sufficiently mixed and dispersed using a ball mill to obtain a paint. Further, the paint was applied to an aluminum plate and dried at room temperature. Then, using an automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd.,
The contact angle of the coating film with water was measured. Further, the contact angle with the nonpolar liquid was measured to measure the solid surface energy.
The results are shown in Table 1.

Examples 2 to 6 With respect to 100 parts by weight of a fluorinated copolymer resin composed of a fluorinated copolymer resin and an acrylic resin in the proportions shown in Table 2, Example 2 was prepared using perfluoro as a fluorinated surfactant. Alkyl carboxylate (trade name: Surflon SC manufactured by Asahi Glass Co., Ltd.)
-101) 1.0 part by weight, Example 3 was 10 parts by weight of a perfluoroalkyl carboxylate (trade name: Surflon SC-101 manufactured by Asahi Glass Co., Ltd.) as a fluorine-based surfactant, and Example 4 was
100 parts by weight of a silicone resin powder having an average particle diameter of 2.0 μm (trade name: Tospearl 120 manufactured by Toshiba Silicon Corporation), Example 5
Is 60 parts by weight of a low molecular weight tetrafluoroethylene polymer powder having an average molecular weight of 8,000 and an average particle diameter of 6.0 μm (trade name: Cefrallube WR manufactured by Central Glass Co., Ltd.), and Example 6 has an average molecular weight of 8,000 and an average particle diameter of A coating material was obtained in the same manner as in Example 1 for 100 parts by weight of a low-molecular-weight ethylene tetrafluoride polymer powder of 6.0 μm (trade name: Sefrallube WR manufactured by Central Glass Co., Ltd.). Further, for these paints, the contact angle with water and the surface energy of the dried coating film were measured in the same manner as in Example 1. The results are shown in Table 1.

Examples 7 to 9 With respect to 100 parts by weight of a fluorinated copolymer resin composed of a fluorinated copolymer resin and an acrylic resin in the proportions shown in Table 2, Example 7 used perfluoro as a fluorinated surfactant. Alkyl carboxylate (trade name: Surflon SC manufactured by Asahi Glass Co., Ltd.)
-101) Silicon resin powder with 10 parts by weight and an average particle size of 2.0 μm (trade name: Tospearl 120 manufactured by Toshiba Silicon Co., Ltd.) 1
In Example 8, the perfluoroalkyl carboxylate (trade name: Asahi Glass Co., Ltd.) was used as a fluorosurfactant.
Surflon SC-101) 10 parts by weight and average molecular weight 8,00
0, 60 parts by weight of a low-molecular-weight ethylene tetrafluoride polymer powder having an average particle diameter of 6.0 μm (trade name: Cefrallube WR manufactured by Central Glass Co., Ltd.), Example 9 is a perfluoroalkylcarboxylic acid as a fluorine-based surfactant 10 parts by weight of salt (trade name: Surflon SC-101 manufactured by Asahi Glass Co., Ltd.) and average molecular weight
A coating material was obtained in the same manner as in Example 1 for 100 parts by weight of 8,000 low-molecular weight ethylene tetrafluoride polymer powder having an average particle diameter of 6.0 μm (trade name: Sefrallube WR manufactured by Central Glass Co., Ltd.). Further, for these paints, the contact angle with water and the surface energy of the dried coating film were measured in the same manner as in Example 1. The results are shown in Table 1.

Examples 10 to 11 With respect to 100 parts by weight of a fluorinated copolymer resin composed of a fluorinated copolymer resin and an acrylic resin in the proportions shown in Table 2, Example 10 was prepared as a perfluorofluorosurfactant. Alkyl carboxylate (trade name: Surflon manufactured by Asahi Glass Co., Ltd.)
SC-101) 8 parts by weight, average molecular weight 8,000, average particle diameter 6.0 μm
60 parts by weight of low molecular weight ethylene tetrafluoroethylene polymer powder (trade name: Sefrallube WR manufactured by Central Glass Co., Ltd.) and silicon resin powder having an average particle diameter of 2.0 μm (trade name: Tospearl 120 manufactured by Toshiba Silicon Co., Ltd.) 40 Parts by weight, Example 11
Is a polyoxyethylene alkyl ether (trade name: Emulgen PP15 manufactured by Kao Corporation) as a nonionic surfactant.
0) 2 parts by weight, 8 parts by weight of perfluoroalkyl carboxylate (trade name: Surflon SC-101 manufactured by Asahi Glass Co., Ltd.) as a fluorine-based surfactant, average molecular weight 8,000, average particle diameter 6.0
μm low molecular weight ethylene tetrafluoride polymer powder (trade name:
A paint was applied to 60 parts by weight of Sefral Lube WR manufactured by Central Glass Co., Ltd. and 30 parts by weight of a silicon resin powder having an average particle diameter of 2.0 μm (trade name: Tospearl 120 manufactured by Toshiba Silicon Co., Ltd.) in the same manner as in Example 1. Obtained. Further, for these paints, the contact angle with water and the surface energy of the dried coating film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 Fluorine resin copolymer resin 70% by weight and acrylic resin 30
A coating material was obtained by mixing 100 parts by weight of an organic solvent, 100 parts by weight of cyclohexanone, 60 parts by weight of butyl acetate, and 40 parts by weight of methyl isobutyl ketone using a ball mill with 100 parts by weight of a fluorine-containing copolymer resin of 100% by weight. Further, for the paint, the contact angle with water and the surface energy of the dried coating film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 With respect to a coating composition comprising an organopolysiloxane resin and an alkali metal compound, the contact angle with water and the surface energy were measured in the same manner as in Example 1. The results are shown in Table 1.

[0024]

[Table 1]

As is apparent from Table 1, the contact angle with water is increased by mixing one or more hydrophobic compounds with the fluorine-containing copolymer resin. That is, it is understood that the solid surface free energy becomes small.

[0026]

The coating composition of the present invention can be applied to the surface of many structures such as bridges, steel towers, buildings, houses, telecommunication facilities, road traffic signs, traffic lights, etc., as well as ships, vehicles, aircraft, etc. in snowy areas. It is useful as a coatable snow and ice protection coating composition.

Continuation of the front page (56) References JP-A-2-228377 (JP, A) JP-A-4-85369 (JP, A) JP-A-5-161875 (JP, A) JP-A-6-122838 (JP) , A)

Claims (1)

(57) [Claims] 1. An organic material comprising, as essential components, 40 to 80% by weight of a fluorocopolymer resin composed of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, and 60 to 20% by weight of an acrylic resin containing methyl methacrylate. Solvent-soluble fluorinated copolymer resin, based on 100 parts by weight of the fluorinated copolymer resin,
0.1 to 2 types of one or more hydrophobic compounds selected from nonionic surfactants, fluorine surfactants, low molecular weight ethylene tetrafluoride polymer powder, and silicon resin powder
A snow and ice-preventing paint composition characterized by mixing with 00 parts by weight.