JPS62252477A - Anti-icing paint composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has a stable, excellent anti-icing performance over a long period of time, consisting of chemically reactive sili cone rubber, a water-repellent compd. and a water-soluble org. compd. CONSTITUTION:100pts.wt. chemically reactive silicone rubber (A) mainly composed of an organosiloxane having a siloxane bond capable of curing by a chemical reaction is blended with 1-80pts.wt. at least one water-repellent compd. (B) selected from the group consisting of silicone oil, mineral oil, petroleum wax, plasticizers, fatty oil and fluorine-contg. oil and 0.01-20pts.wt. at least one water-soluble org. compd. (C) selected from the group consisting of surfactants (e.g., alkylbenzenesulfonates), polyhydric alcohols (e.g., glycerol) and water-soluble resins (e.g., PVA).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to anti-icing and snow coatings, and more specifically, the present invention relates to anti-icing and snow coatings, and more specifically, the present invention is based on a chemically reactive silicone rubber (hereinafter simply referred to as silicone rubber), which is coated with a water-repellent compound. The present invention relates to an anti-icing and snow coating characterized by being formed by mixing it with an organic water-soluble compound.

[Conventional technology]

In the winter, in the cold region, transportation systems such as ships, vehicles, and aircraft, as well as marine and land structures, often become unable to operate or malfunction due to ice and snow buildup, resulting in accidents that even result in loss of life. Therefore, it is necessary to perform ice and snow removal work, but this work requires a great deal of labor and expense. As a countermeasure, we apply fluororesin, silicone resin, and acrylic resin to the surface of objects.

Method C has been trialled to reduce the ice-forming force and reduce the labor required for removing ice and snow by coating with urethane resin-based, vinyl resin-based, etc. paints. For example, US Pat. No. 4,271,215
(1981) discloses an anti-icing coating comprising a silane coupling agent and an organic titanium salt. Further, JP-A No. 58-132073 proposes an anti-snow paint made by adding silicone oil or wax to vinyl resin, acrylic resin, nitrified cotton lacquer, or the like. Further, JP-A No. 59-25868 proposes an anti-icing material composition made by adding a lithium compound to an organopolysiloxane resin.

[Problem to be solved by the invention 3] The phenomenon of freezing and snowing occurs when a thin water film interposed between ice or snow and the surface of an object adheres and freezes due to molecular adsorption forces such as van der Waalska and hydrogen bond forces. It is caused by doing. In order to reduce the icing force,
Intermolecular adsorption forces, so-called low-polar material forces such as permanent dipoles, induced dipoles, and hydrogen bond forces, must exist continuously on the surface of objects. However, when we conducted a follow-up study on the above-mentioned disclosed techniques, we found that the coatings on the surfaces of objects made of these coating compositions showed considerable wear resistance for 1 to 2 months after application compared to the coatings of general external coatings. Although the ice and snow prevention effect can be obtained, the effect tends to decrease after that. There is a need for the development of anti-icing and snow coatings that have a long-lasting effect.

Therefore, an object of the present invention is to provide an anti-icing coating that can provide stable and excellent anti-icing ability over a longer period of time.

(Means for Solving the Problems) As a result of physicochemical and surface chemical research on the phenomenon of ice or snow accretion, the present inventors found that on the surface of an object to which water or snow adheres, hydrophobic molecules and hydrophilic molecules The present invention was completed by obtaining the knowledge that the adhesion force of ice and snow becomes extremely small in a surface state in which the molecular forces j are mixed in an appropriate distribution.

The present invention is characterized by the use of a composition obtained by mixing (a) silicone rubber, (b) a water-repellent compound, and (c) an organic water-soluble compound.

Therefore, the content of the present invention will be explained in detail below.

(a) Silicone rubber The main component is Orga-7y/siloxane having a siloxane bond that hardens through a chemical reaction, and the Orga-7siloxane has a hydroxyl group, an alkoxy group, etc. as a curing-reactive functional group, and a methyl group, as an organic group. A phenyl group, a vinyl group, etc. are directly bonded to Si. In addition, a polyfunctional silane compound in which a hydrolyzable group (e.g., acetoxy group, ketoxy group, ketosim group, etc.) is bonded to organosiloxane is used as a crosslinking agent, and a metal organic acid salt (e.g., dibutylsilaurylate, tin dioctenoate) is used as a crosslinking agent. , iron stearate, lead octylate, peroxide, organic amine, etc.) as a curing catalyst, and by blending at least one of these, it can be made into a one-pack type or a two-pack type. Furthermore, it is also possible to use a room temperature curing type or a heat curing type. Ninara silicone rubber cures at room temperature or by heating through chemical reactions such as hydrolysis, dealcoholization, acetic acid removal, deatonation, deaminerization, and deoxime removal, f, and ease of application. Most preferred is a silicone rubber that is in liquid form and hardens at room temperature.

As an example of the above silicone rubber, KE12
12. KE1800. KE68. KE42S, KE45
．． KE45TS, KE445. KE348 (all trade names of Shin-Etsu Chemical Co., Ltd.) etc. can be used.

(b) Water-repellent compound The water-repellent compound in the present invention may be any one of silicone oil, mineral oil, petroleum wax, plasticizer, fatty oil, fluorine oil, etc., whether it is liquid or grease-like at room temperature, but especially Silicone oil is most preferred. Silicone oil is methyl silicone oil,
Methylphenyl silicone oil may be used alone or as a mixture of both.

These silicone oil equivalents include KF96.
KF92. KF69 (more than methyl silicone oil),
KF50. KF53. KF54°KF56 (all methylphenyl silicone oils, both trade names of Shin-Etsu Chemical Co., Ltd.) can be used.

(c) Organic water-soluble compound Any organic compound may be used as long as it is soluble in water at room temperature, solid or liquid, and has good mixing and dispersibility in silicone rubber. Equivalent products include cationic surfactants, anionic surfactants, nonionic surfactants, 9 amphoteric surfactants, polyhydric alcohols, water-soluble resins, etc. These compounds may be used alone or in a mixture of two or more. Examples of substances corresponding to each compound are listed below.

(1) Cationic surfactant alkyltrimethylammonium halide, imigzolinium chloride, alkylpyridinium halide, benzethonium chloride (2) Anionic surfactant alkylbenzene sulfonate, alkyl ether carboxylate, polyoxyalkyl 7-ethyl chloride ether sulfate, alkali metal salt of saturated or unsaturated fatty acid (3) Nonionic surfactant polyoxyethylene alkyl ether tan fatty acid ester, polyoxyethylene fatty acid amide, dimethylpolysiloxane/polyoxyalkylene copolymer, vinylpolysiloxane・Polyoxyalkylene copolymer, hexafluoropropene oligomer derivative (4) Amphoteric surfactant Ami-7 carboxylate, alkyl betaine, imigzolinium betaine (5) Polyhydric alcohol glycerin, ethylene glycol, propylene glycol, polyethylene Glycol (6) Water-soluble resin Polyvinyl alcohol, carboxyl methyl cellulose, hydroxyethyl cellulose, polyethylene oxide, polyacrylamide The anti-icing and snow coating of the present invention mainly contains each of the components described in (a), (b) and (c) above. The concrete composition method is as follows. All constituent proportions are shown in parts by weight.

(1) 1 to 80 parts, preferably 5 to 70 parts, of silicone oil are mixed with 100 parts of solid content of silicone rubber, and the mixture is thoroughly stirred with a stirrer in a container until the whole is homogeneous. When these proportions are less than 4 parts, the anti-icing and snowing performance is extremely reduced, and when it is more than 80 parts, the coating film becomes weak and remains sticky, which is not practical.

The silicone oil is methyl silicone oil or methylphenyl silicone oil, and suitably has a viscosity (at 25° C.) of 1.0 to 1,000,000 centistokes, preferably 10 to ioo, ooo centistokes. 1.0 centistokes or less and i,ooo,o
If the viscosity is more than oo centistokes, the anti-icing and snow-preventing property is poor.

Silicone oils may be used alone or in mixtures such as methyl silicone oil or methylphenyl silicone oil,
Methyl silicone oil, methylphenyl silicone oil, a mixture of methyl silicone oils, and a mixture of methyl phenyl silicone oils are used. Among these oils, at least two kinds of silicone oils are used in the mixed oil, and the total amount thereof does not exceed the above mixing ratio.

(2) Next, 0.01 to 20 parts, preferably 0, of an organic water-soluble compound is added to the mixture of (1) above.

Mix 1 to 10 parts and stir well in a container with a stirrer until the whole is homogeneous. Organic water-soluble compounds: 0.0
If the amount is less than 1 part, the anti-icing performance will be reduced, and if it is more than 20 parts, the water resistance of the coating will be poor and there will be no difference in performance, which will be disadvantageous in terms of cost. After mixing the above components, organic solvents (for example, at least one selected from Doolol, Kijilor, and mineral spirits), coloring pigments, extender pigments, anti-sagging agents, etc. may be mixed as necessary. can.

The coating composition thus prepared can maintain excellent anti-icing and snow performance over a long period of time. The reason for this is that by further mixing an organic water-soluble compound into the mixture of silicone rubber and silicone oil, the water repellency of the coating surface and its durability are increased.

This will be explained more specifically as follows.

When ice and snow containing water adhere to the surface of the coating film, the contact occurs in a microscopic and intermittent manner due to the proofing properties of silicone rubber. The coating film in contact with moisture first acts on the hydrophilic organic water-soluble compounds among the silicone oil and organic water-soluble compounds that are dispersed in a microphase-separated state in the coating composition. It is thought that silicone oil is extracted when the aqueous solution produced by this transfers to the coating surface. This phenomenon is particularly noticeable in the case of mixtures of surfactants.This phenomenon is caused by the fact that surfactant ions associate, form micelles, and are oriented on the coating surface. They begin to arrange on the surface in place of water molecules, which have high energy.

In addition, at this time, the silicone oil coexisting inside the coating film has an affinity with the highly lipophilic hydrophobic groups inside the micelles, so that the molecular force C of the silicone oil increases as the surfactant moves between the hydrophobic groups. Arranged on the coating surface. As a result of both of these effects, the hydrophobic molecules of the surfactant and silicone oil are arranged on the coating surface, resulting in the formation of a non-polar, water-repellent, low-temperature fluid surface layer that prevents ice and snow from van der Waalska and As the molecular adsorption force due to hydrogen bonding force is weakened and low-temperature slip properties are increased, excellent anti-icing and snow performance can be obtained. In addition, as long as the outermost layer of the paint film is constantly covered with a hydrophobic molecular film and its strength is not exhausted, organic water-soluble compounds and silicone oil remain in the paint film, and when it comes into contact with moisture, Since only a small amount of water leaches out, a long-lasting car can be obtained.

(Example) Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples. In addition, the composition values described in Examples and Comparative Examples are shown in parts by weight, and the weight % is also written in parentheses.

Examples and Comparative Examples Composition examples of the present invention are shown in Table 1, and comparative examples are also listed. Comparative Example 1 is a mixture of silicone rubber and only methylphenyl silicone oil, and Comparative Example 2 is an oil-based external paint (Evamarin 2L...trade name) manufactured by Kanto Toyama.

Test Example 1 An epoxy resin paint was applied to one side of a 70 x 150 x 3 mm steel plate, and then the paint of each composition example listed in Table 1 was overcoated, and the test piece was dried at room temperature for 7 days. At this time, the dry film thickness of each composition side paint was approximately 50 μm. Next, the icing power was measured using the testing machine shown in FIG. The measurement procedure is as follows. That is, a test piece 1 coated with the paint of the present invention is placed on a base plate 2. The test piece is fixed by a protrusion on the rear end of the plywood. A holding plate 3 having a through hole in the center is placed directly above the test piece, and an aluminum cylinder 4 (inner diameter 40 mm, outer diameter 47 mm, height 4
After pouring distilled water into the cylinder to a height of 20 nm, it was left in a -20°C freezer for 5 hours. Then, in the freezer, the gear 6 of the tester was gradually rotated by power while shearing force was applied to the adhesive surface between the water and the paint film, and the load when the adhesive surface separated was measured using a rotor self, and the shear peel strength ( Unit: kgf/cro2) was calculated and evaluated. Further, after each of the test pieces described above was exposed outdoors for 6 months, a similar test was conducted to evaluate the sustainability of the anti-icing performance. These results are shown in Table 2.

Test example 2 The paints of Composition Examples 1 and 9 were applied to a cod fishing boat in northern Japan.

It was applied to masts, handrails, etc. (dry film thickness 50 μm) and rubbed for 3 months, but the deicing work that previously required 5-6 times a day was reduced to 4-2 times. Furthermore, since the ice can be removed with only a small amount of impact force, it has been found that the crew's labor is considerably reduced.

As explained above, it is clear that the anti-icing and snow coating according to the present invention exhibits excellent performance over a long period of time.

[Brief explanation of drawings]

FIG. 1 is a sectional view of an apparatus for testing the water adhesion of the anti-icing and snow coating of the present invention. 10. Test piece 60. 200 gears plate 79. Load cell 30. Holding plate 80. Ball bearing 40. Aluminum 90. Steel cylinder 50. Distilled water (ice) or more

Claims (1)

[Scope of Claims] 1. An anti-icing and snow coating composition comprising a mixture of a chemically reactive silicone rubber, a water-repellent compound, and an organic water-soluble compound. 2. Scope of the Claims In claim 1, the mixing ratio of the water-repellent compound is 1 to 80 parts by weight, and the mixing ratio of the organic water-soluble compound is 0.1 to 100 parts by weight of the chemically reactive silicone rubber.
An anti-icing and snow coating composition characterized in that the amount is 01 to 20 parts by weight. 3. In claim 1, the water-repellent compound is at least one selected from silicone oil, mineral oil, petroleum wax, plasticizer, fatty oil, fluorine oil, etc. Paint composition. 4. The anti-icing and snow coating composition according to claim 1, wherein the organic water-soluble compound is at least one selected from surfactants, polyhydric alcohols, water-soluble resins, etc. .