JPH07331114A - Film forming composition for icing and peeling - Google Patents

Abstract

(57) [Abstract] [Purpose] Regarding the composition that forms a film that is effective in preventing icing and removing icing, by using various resin components as binders without selecting special resin components. Provided is a composition that forms a film having excellent anti-icing and anti-icing effect. [Structure] (a) Hydrophobizing treatment with a hydrophobizing agent having an organic group, and the hydrophobizing treatment rate (carbon weight conversion) is 1.
5 to 75 wt% of hydrophobizing filler, which is 7 wt% or more,
(B) A film-forming composition for icing / peeling, which comprises 25 to 95% by weight of a binder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition for preventing icing and for icing and peeling, which has excellent effects for preventing and icing on various substrates.

[0002]

2. Description of the Related Art The following compositions are known as compositions which are coated on various base materials to form a film and have an anti-icing effect.

That is, Japanese Patent Application Laid-Open No. 58-65779 discloses a composition for preventing icing comprising a specific organopolysiloxane resin and a specific alkali metal compound.
No. 0-206888 discloses a composition for preventing icing, which comprises a specific organopolysiloxane resin, a specific alkali metal compound and liquid or solid paraffin, and Japanese Patent Application Laid-Open No. 61-51069 discloses a specific organopolysiloxane. An anti-icing composition comprising a polysiloxane resin, a specific alkali metal compound and a hydrophobic silicon compound having a carboxyl group is disclosed.

Further, JP-A-62-252477 discloses that a coating composition comprising a chemically reactive silicone rubber, a specific water-repellent compound and an organic water-soluble compound has an effect of preventing snow accretion. JP-A-3-84069 discloses that a paint containing a specific organopolysiloxane copolymer and a hydroxyl group-containing resin has an anti-icing effect.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a resin composition which forms a coating film effective in preventing icing and removing icing from various resin components without selecting a special resin component. An object of the present invention is to provide a composition which forms a film having excellent ice accretion prevention and ice accretion peeling effects when used as a binder.

[0006]

Means for Solving the Problems The present invention provides (a) a hydrophobizing treatment with a hydrophobizing agent having an organic group, the hydrophobizing rate (carbon weight conversion) being 1.7% by weight or more. 5 to 75% by weight of filler, and (b) binder 25 to 95
% Of the coating composition for icing and debonding. The hydrophobizing agent having an organic group is a compound having a reactive group and an organic group in one molecule, as long as it can treat the filler particles and bond the organic groups to the filler particles. It is not particularly limited.

Incidentally, the term "for removing ice accretion" as used in the present invention means having a function of preventing ice accretion and a function of easily exfoliating ice accretion, and the composition of the present invention is used for that purpose. It is what is done. Then, the above-mentioned Japanese Patent Laid-Open No. 58
-65779, page 5, JP-A-60-206888
As can be seen in JP-A Nos. 5-6, JP-A-62-252477, page 4, JP-A-3-84069, etc., in this technical field, the anti-icing property and the anti-icing property are defined. It is recognized that the relationship between the front and back is one, and that the effect of anti-icing property is also recognized by the data of the anti-icing property.

Examples of the hydrophobizing agent having an organic group include trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, tri-n-butylchlorosilane, tert-butyldimethylchlorosilane, n-butyldimethylchlorosilane and octadecyldimethyl. Chlorosilane, trimethylmethoxysilane, trimethylethoxysilane, chloromethyltrimethylsilane, hexamethyldisilazane, 1- (3-chloropropyl) -1,1,3,3,3-pentamethyldisiloxane, 1-chloromethyl-1 , 1,3,3,3-pentamethyldisiloxane, trifluoropropyldimethylchlorosilane, tridecafluorooctyldimethylchlorosilane, trifluoropropyldimethylmethoxysilane,
A silane system such as tridecafluorooctyldimethylmethoxysilane, and one -H group, -Cl group, -O at one end.
R (R: H or C _n H _{n + 2} , n = 1 to 4 integer) group,
A silicone system of polydimethylsiloxane having a reactive functional group such as CH—CH ₂ group, and trifluoroethyl-
There are fluorine-based compounds such as iodide and hexafluoropropylene oxide, and aliphatic hydrocarbon-based compounds such as alkyl chlorides. Particularly, trimethylchlorosilane, octadecyldimethylchlorosilane, hexamethyldisilazane, one -H group at one end, and -Cl group. And the like are preferred.

In particular, as the hydrophobizing agent, the formula in the molecule is

Embedded image Those having a group represented by —X (CR ₃ ) ₃ (wherein, X is Si or C, and R is hydrogen or fluorine) are preferable.

Hydrophobization treatment rate (converted to carbon weight) (S)
Is the ratio of the weight of carbon atoms contained in the organic group bonded to the filler by the hydrophobic treatment to the weight of the hydrophobic-treated filler, and is represented by the following formula.

[Equation 1] And specifically, it is defined as follows. Weight of the filler treated to be hydrophobic: P Weight of organic group bonded to the filler by hydrophobic treatment: L Ratio of carbon atoms to weight of organic group bound to the filler by hydrophobic treatment: C

[Equation 2]

[0011] Incidentally, where the filler particles, and the combined organic group such hydrophobizing agent is Me ₃ SiNHSiMe _3, when the filler is assumed to be the case of silica, Me ₃ S
iNHSiMe ₃ is hydrolyzed and Si-
When bound to become Si-O-SiMe ₃ in OH -
Refers to SiMe ₃ . In addition, the hydrophobizing agent

[Chemical 3] And assuming that the filler is silica,

[Chemical 4] Hydrolyzes and binds to Si-OH on the silica surface

[Chemical 5] When

[Chemical 6] Refers to.

The hydrophobized filler particles used in the present invention are required to have a hydrophobization treatment rate (calculated by carbon weight) of 1.7% or more. It is necessary that the ratio is in the range of 5 wt% or more and 75 wt% or less. The hydrophobic treatment rate is preferably 2% or more, and more preferably 3% or more. The blending amount of the hydrophobically-treated filler particles is preferably 10 wt% or more, and more preferably 15 wt% or more.

If the above conditions are exceeded, a sufficient icing / separation effect (an effect of icing / desorption time of 35% or less as compared with the case where the composition of the present invention is not applied) cannot be obtained, and Even if the hydrophobic treatment rate (converted to carbon weight) is 1.7% or more, if the proportion in the composition is 75% by weight or more, the film properties deteriorate and the practicality is greatly deteriorated.

As the filler particles used in the present invention (before being subjected to the hydrophobizing treatment), filler particles usually mixed with a resin or an elastomer can be used, and specific examples thereof include silica and alumina. , Ferric oxide, titanium dioxide,
Examples thereof include zinc oxide, calcium carbonate, barium carbonate, cobalt carbonate, calcium silicate, magnesium silicate, copper oxide, cobalt oxide, carbon black, silicone resin, acrylate copolymer and styrene polymer.

Of these, those having --OH on their surface are preferred, and Si--OH and A are more preferred.
Silica or alumina having a large amount of 1-OH is selected.

The particle size of the filler particles is not particularly limited, but is preferably 10 μm or less, more preferably 1 μm or less.

The binder may be at room temperature or
As long as it is a non-water-absorbing organic substance that forms a film by heating, it is not limited to silicone resin, fluororesin, etc., and a wide range of thermoplastic or thermosetting resins or elastomers may be used alone or in combination. You can

For example, so-called ordinary resins and elastomers can be used except for water-absorbing resins such as cellulose type and (meth) acrylic acid type. Of course, a curing catalyst and a vulcanizing agent may be used together with these components, if necessary.

Specific resins and rubbers include polyethylene, polypropylene, polystyrene, ABS, AS and E.
VA, ionomer, polymethylpentene, polyvinyl chloride, polymethyl acrylate, polyvinyl acetate, polyacrylonitrile, polyvinyl alcohol, polycarbonate, polyester, nylon, polyarylate, polysulfone, polyether sulfone, polyether ketone,
Fluoroplastic, melamine resin, phenolic resin,
Urethane resin, epoxy resin, unsaturated polyester, diacryphthalate, mixed resin of epoxy and phenol,
Polyacrylonitrile and epoxy mixed resin, urethane rubber, fluororubber, butyl rubber, polysulfide synthetic rubber, olefin synthetic rubber, nitrile rubber, silicone rubber, silicone resin, fluororesin, butadiene synthetic rubber, and the like. It is not limited.

The composition of the present invention is produced by mixing the organic binder and the hydrophobized filler particles. This mixing may be mixed during the manufacturing process of the curable composition. The mixing means is arbitrary, for example, a sand mill mixing method, a ball mill mixing method, a tumbler mixing method,
A stirring mixing method or the like can be used.

If desired, a solvent may be added to the composition of the present invention to dilute it. For example, the concentration of the active ingredient of the composition can be controlled for the purpose of improving the workability of coating and impregnation treatment or adjusting the film thickness after forming a film. Examples of such a solvent include alcohols, ketones, aromatics, ethers, hydrocarbons, etc., but it is necessary to select them in accordance with the resin to be used.

If desired, appropriate additives can be added to the composition of the present invention. For example, by adding a curing accelerator, the time required for forming a film of the composition can be shortened. This curing accelerator includes dibutyltin diacetate, a platinum complex, an amine-based catalyst, etc., and is mixed in a ratio of, for example, 2% by weight or less with respect to the composition.

The composition of the present invention is used by applying or impregnating a base material which requires an ice accretion preventing or ice accretion removing effect by an appropriate means to form a film. Upon coating or impregnation, it is possible to adjust the concentration by diluting with a solvent in order to obtain suitable film forming properties as described above. As means for applying and impregnating, dip coating and impregnation method, roll coating,
A brush coating method, a spray method, etc. can be used.

The material of the base material to which the film formation composition for icing and peeling of the present invention is applied is not particularly limited, and may be a metal,
It can be applied to substrates made of various substances such as plastics, inorganic materials, rubber, glass and fibers.

The embodiments of the present invention are listed below. (1) (a) Hydrophobizing treatment with a hydrophobizing agent having an organic group, and the hydrophobizing filler has a hydrophobizing treatment rate (carbon weight conversion) of 1.7% by weight or more and 5 to 75% by weight, and ( b) A film forming composition for icing / peeling, comprising 25 to 95% by weight of a binder. (2) The hydrophobizing agent has a formula in its molecule.

Embedded image -X (CR _{3) 3} (wherein, X is Si or C, R is hydrogen or fluorine.) Preceding those having a group represented by (1) icing peeling according Film forming composition. (3) The film forming composition for ice accretion peeling according to the above (1) or (2), wherein the filler has an OH group on the particle surface. (4) The film forming composition for ice accretion peeling according to (1), (2) or (3) above, wherein the hydrophobic treatment rate is 2.0% by weight or more. (5) The film formation composition for ice accretion peeling according to the above (1), (2) or (3), wherein the hydrophobic treatment rate is 3.0% by weight or more. (6) The film formation composition for ice accretion peeling according to the above (1), (2), (3), (4) or (5), wherein the component (a) is 10% by weight or more. (7) The film forming composition for ice accretion peeling according to (1), (2), (3), (4) or (5), wherein the component (a) is 15% by weight or more. (8) The preceding paragraphs (1), (2), (3), (4), (5),
A method for coating a film for deicing and icing, which comprises coating a substrate with the composition according to (6) or (7).

[0026]

EXAMPLES a, b, obtained by a dry method or a wet method
Each of the c, d, e, f, and g silica particles was hydrophobized with various hydrophobizing agents shown in Table 2 so that the hydrophobizing treatment rates (calculated by carbon weight) shown in Table 2 were obtained. Table 2 also shows the specific surface area and particle diameter of the particles obtained by the treatment.

Measurement of Hydrophobization Treatment Ratio (Carbon Weight Conversion) in Examples (In the Case of Silica) Measurement of Hydrophobization Treatment Ratio of Silica (Carbon Weight Conversion) Induction Thermal Absorption Infrared Absorption Method (Using Reco CS-344) 0.5g of sample (hydrophobized silica) is set in the test equipment, radiated with high frequency and ignited to about 2000 ° C.
All carbon compounds are converted to CO ₂ gas (ignition time is about 1
Minutes, including the nitrogen purge time, about 2 minutes). The generated CO ₂ gas is quantified by infrared absorption spectrum to measure the carbon content. The measurement was performed 3 times and the average value was calculated. From the carbon content and the sample weight, the hydrophobization treatment rate (in terms of carbon weight) after the hydrophobization treatment was calculated.

The carbon content of silica not subjected to the hydrophobizing treatment is shown. As shown in Table 1, in the silica not subjected to the hydrophobizing treatment, the carbon content is extremely small.

[0029]

[Table 1] As shown in Table 2 below, the treated particles of types a and c are obtained by subjecting the particles of type X to a hydrophobic treatment. The treated particles of type g are obtained by subjecting the particles of type Y to a hydrophobic treatment. The types b, d, e, and f are the types X described above.
Particles that are neither N nor Y are treated, but untreated particles are similar to X and Y.

[0030]

[Table 2] (Note) (a) Me ₃ SiNHSiMe ₃ (b) Cl ₂ SiMe ₂ (c) Polydimethylsiloxane [Cl (CH at one end
₃ ) having ₂ Si-] (d) C ₈ H ₁₇ SiCl ₃

Hydrophobized filler particles a shown in Table 2
~ G in solid content of 40% by weight, epoxy resin paint 6
A film-forming composition was prepared by thoroughly mixing and mixing 0% by weight with a tabletop sand mill. Then, an ice accretion desorption experiment was conducted by the following test method. The results are shown in Tables 3 and 4.
Table 3 clarifies the relationship between the hydrophobization rate of the filler and the ice accretion / desorption time, and Table 4 reveals the relationship between the filler addition amount and the ice accretion / desorption time.

<Test Method> (1) The inner surface of a cylindrical aluminum container (height: 40 mm, diameter: 27 mm) was degreased, and this container was immersed in the film forming composition to uniformly treat the inner surface of the container. The treatment conditions were heat curing at 200 ° C./30 minutes. The film thickness of the formed film was about 0.5 μm. (2) A fixed amount (10 ml) of distilled water in the treated container.
It was put in a freezer at −20 ° C. and completely frozen. (3) Remove the container from the freezer and set it under certain conditions (25
In an environment of ℃, humidity 44%), put the container upside down,
The time taken for the ice in the container to fall was recorded.

[0033]

[Table 3] * It did not fall as ice, everything melted into water, and it fell as water droplets. The types and blanks in Table 3 are as follows. The types a to g are shown in Table 2. Type h: 200 ° C / 3 for methyl silicone resin only
Bake in 0 minutes. Blank: Water was directly put into an aluminum container without any treatment for freezing.

[0034]

[Table 4] * It did not fall as ice, everything melted into water, and it fell as water droplets.

[0035]

【The invention's effect】

(1) By adopting the composition according to the present invention, the selection of binders has become extremely diverse, so that a film for ice accretion release which is most suitable for the substrate to which the composition is applied and the environment can be formed. (2) The composition of the present invention can be applied by any method such as coating, impregnation and spraying. (3) According to the film for peeling off ice accretion obtained by the composition of the present invention, it is possible to reduce the de-icing time to 35% or less as compared with the case where the composition of the present invention is not applied.

Claims (3)

[Claims] 1. A hydrophobic filler 5 to 75% by weight, which is (a) hydrophobicized by a hydrophobizing agent having an organic group and has a hydrophobic treatment rate (converted to carbon weight) of 1.7% by weight or more.
And (b) 25 to 95% by weight of a binder. 2. The hydrophobizing agent is represented by the formula: —X (CR ₃ ) ₃ (wherein X is Si or C and R is hydrogen or fluorine) in its molecule. The film-forming composition for icing / peeling according to claim 1, which has a group represented by the formula: 3. The film-forming composition for ice accretion peeling according to claim 1, wherein the filler has an OH group on the particle surface.