JP2003147202A - Silicon component- and fluorine component-containing composition and ice and snow accretion preventing member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicon component- and fluorine component-containing composition having ice and snow accretion preventing effects during snowfall and low temperatures and snow sliding performances during a temperature rise in combination. SOLUTION: The silicon component- and fluorine component-containing composition for a coating film or a film comprises at least a specific silicon-containing compound and a specific fluorine-containing compound and, if necessary, another silicon-containing compound in an amount of <=25 pts.wt. based on 100 pts.wt. (expressed in terms of SiO2 ) of the specific silicon-containing compound. When the composition is formed into the coating film or film, the surface free energy (γ) or the surface thereof at 25 deg.C is 5-24 [mN/m] and the ratio (γd/γp) of the dispersion force component (γd) to the nondispersing force component (γp) is 8.5-20. The ratio of increase in the surface energy radio before and after an immersion treatment of the coating film or film at 90 deg.C for 5 min is within 1.5 times.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition containing a silicon component and a fluorine component, and a snow ice prevention member.

[0002]

2. Description of the Related Art Conventionally, ships, offshore structures, aircraft,
In various fields such as vehicles, houses, and power transmission towers, various anti-snow / ice prevention paints have been studied for the purpose of preventing damages caused by snow and freezing.

In particular, there are many proposals for the use of organopolysiloxane which exhibits an effect of preventing snow accretion for the following reasons. That is, in the case of an organopolysiloxane, when it is formed into a coating film or a film, hydrocarbon chains are arranged on the surface to form a water repellent surface with low surface energy, and since the glass transition temperature is low, it is -30 ° C or lower. However, its molecular motion is not frozen, and it is difficult to form hydrogen bonds during freezing.

JP-A-2-147688 proposes a composition using a specific alkoxydimethylsiloxane, and JP-A-3-84069 discloses a composition in which organopolysiloxane bleeds out or ice is released. A composition in which a hydroxyl group-containing resin is used in combination with a copolymer obtained from a specific organosilicon compound having a hydrolyzable silyl group and another monomer in order to improve the low durability of the snow and ice prevention effect by peeling with Things have been proposed.

[0005]

However, it cannot be said that the above-mentioned conventionally known compositions have a sufficient effect of preventing snow accretion. Further, the effect of preventing snow accretion is required at the time of snowfall, but after the snowfall, the snow sliding property is desired for the following reasons. That is, when the temperature rises after snowfall, the snowfall on the surface of the structure such as the roof of the building gradually changes into a solid snow-like state containing a lot of water. Then, such solid snow adheres to the surface of the structure and is difficult to peel off, that is, the snow sliding property is deteriorated. Therefore, in such a state, improvement in snow sliding property is desired. If the slope of the structure is less than 45 °, it is likely to snow. Therefore, it is particularly desired that the snow sliding property is excellent.

[0006]

In view of the above situation, the present inventors have earnestly studied in order to provide a composition having both the effect of preventing snow accretion during snowfall and low temperature and the snow sliding performance during temperature rise. As a result, we obtained the following findings. That is, a composition having an excellent effect of preventing snow accretion during snowfall does not necessarily have an excellent snow sliding property. Specifically, the smaller the adhesion force (ice accretion force) between the snow and the surface of the structure, the more advantageous it is to prevent snow accretion. In addition, it is considered that the presence of water at the interface between snow and the structure facilitates snow sliding due to the viscosity (lubrication effect) of water.
Conventionally known anti-icing agents have a low surface hydrophilicity and a small snow sliding effect.

However, in the composition containing a silicon component and a fluorine component, the surface free energy (γ) when formed into a coating film or a film is in a specific range, and the dispersion force component (γ ^d ) in the surface free energy and the non-dispersion component. When the ratio (γ ^d / γ ^p ) to the force component (γ ^p ) is in a certain range, an excellent effect of preventing snow and ice is exhibited.

The present invention has been completed based on the above findings, and the first gist of the present invention is to contain at least an A component and a B component defined below, and further, if necessary, A
A coating composition containing a silicon-containing compound other than the component A in a ratio of 25 parts by weight or less relative to 100 parts by weight of the component (converted to SiO ₂ ) or a composition containing a silicon component and a fluorine component for a film, the coating film Or when made into a film,
Surface free energy (gamma) is 5 to 24 at 25 ° C. of the surface is [mN / m], the surface dispersion force component in the free energy (gamma ^d) a non-dispersive force component (gamma ^p) and the ratio of (gamma ^d / Γ ^p ) is 8.5 to 20, and the increase rate of the surface free energy before and after the immersion treatment of this coating film or film at 90 ° C. for 5 minutes is 1.5 times or less. In the composition containing a silicon component and a fluorine component.

<Component A>: Tetraalkoxysilane (a
1), its partial hydrolysis-condensation product (a2), tetraalkoxysilane and / or 1 selected from the group of hydrolysis-condensation products (a3) obtained by adding more than the theoretical amount of water to the partial hydrolysis-condensation product. More than one compound <Component B>: Fluorine-containing compound

A second aspect of the present invention resides in a snow-ice prevention member having a surface formed of the above composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention comprises a silicon component and a fluorine component-containing composition for a coating film or film containing an A component defined below as a silicon component and a B component defined below as a fluorine component. It is a thing.

In the present invention, tetraalkoxysilane (a1), its partially hydrolyzed condensate (a2), tetraalkoxysilane and / or its partially hydrolyzed condensate, as component A, is added with water in an amount not less than the theoretical amount of water. One or more compounds selected from the group of the resulting hydrolysis-condensation products (a3) are used.

The above tetraalkoxysilane (a1)
Is an organic ester of orthosilicic acid Si (OH) ₄ , which is represented by the general formula Si (OR) ₄ (where R represents an alkyl group) and is also called a tetraalkyl silicate. It is also sometimes simply called alkyl silicate.

As the alkyl group in the above general formula, for example, a linear, branched or cyclic alkyl group,
Specifically, a methyl group, an ethyl group, an n-propyl group, i
Examples include -propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, neopentyl group, hexyl group and octyl group. Also,
It may be a fluorinated alkyl group obtained by substituting a part of hydrogen atoms of these alkyl groups with a fluorine atom. Further, each alkyl group may be the same or different.

Particularly, an alkyl group having 1 to 4 carbon atoms is preferable. A methyl group and / or an ethyl group is preferable from the viewpoint of snow-sliding property, and it is more preferable that all alkyl groups are methyl groups. In the case of an alkyl group having a carbon number of more than 4, the amount of the organic solvent necessary for forming the composition of the present invention into a uniform coating composition may be large, and the hydrolyzability is poor. S in outdoor exposure of the resulting coating
The production of iOH groups (silanol groups) becomes extremely slow,
The expression of snow sliding performance tends to decrease.

In the present invention, as the tetraalkoxysilane (a1), tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec- Butoxysilane or tetra t-butoxysilane is preferably used.

Examples of the partially hydrolyzed condensate of tetraalkoxysilane (a2) include, for example, polymethoxypolysiloxane which is a partially hydrolyzed condensate of tetramethoxysilane as "MKC silicate MS5" manufactured by Mitsubishi Chemical Corporation.
1 ”,“ MKC silicate MS56 ”and the like.

The hydrolyzed condensate (a3) obtained by adding more than the theoretical amount of water to the tetraalkoxysilane and / or its partial hydrolyzed condensate can be obtained as a hydrolyzed solution of each of the above components. Here, the theoretical amount of water is
The amount of water is 0.5 times the molar amount of the alkoxy group, and the amount of water equal to or more than the theoretical amount of water is 0.
A 5 to 1 molar amount of water is preferred.

Among the above-mentioned component A, tetramethoxysilane and / or its partially hydrolyzed condensate have high hydrolysis reactivity and easily form silanol groups. Therefore, these, the amount of the solvent described below used to prepare a uniform liquid composition may be small, does not correspond to a dangerous substance, because it is possible to easily obtain a composition having a high snow sliding effect, It is particularly suitable.

The composition of the present invention comprises the above-mentioned component A (Si
As the silicon-containing compound other than (OR) ₄ etc.), for example, a silicon compound having an organic group directly bonded via silicon can be contained.

Examples of the silicon compound include various silane coupling agents. In particular,
Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxy Silane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriiso Propoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 Glycidoxypropyl triethoxysilane, 2- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Trialkoxy such as mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Examples thereof include silane compounds.

Further, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane,
Diphenyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropylmethyldioxysilane, N- (2-aminoethyl)- Examples thereof include dialkoxysilane compounds such as 3-aminopropylmethyldimethoxysilane.

Further, methyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, dimethylchlorosilane, methylvinyldichlorosilane, 3-chloropropylmethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, etc. The chlorosilane compound of.

Furthermore, 3-aminopropyltrimethoxysilane, N-3-trimethoxysilylpropyl-m-phenylenediamine, N, N-bis [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis. Examples include [3- (trimethoxysilyl) propyl] ethylenediamine and P- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane. Moreover, the partial hydrolysis-condensation product of each said compound is mentioned.

Silicon-containing compounds other than the component A (Si (OR) ₄ etc.) have a smaller amount of hydrolyzable functional groups than the component A and contribute to the expression of snow sliding property remarkably.
Therefore, when such a silicon compound is used, the usage ratio is 25 parts by weight or less (preferably 10 parts by weight or less) with respect to 100 parts by weight of the component A (Si (OR) ₄ etc.) (provided that it is converted into SiO ₂ ). Limited to.

In the present invention, a fluorine-containing compound is used as the B component. As the fluorine-containing compound, a fluorine-containing silane coupling agent, a fluorine-containing surfactant,
Fluororesin powder is preferably used. Among these,
A fluorine-containing silane coupling agent is preferable, and as the fluorine-containing silane coupling agent, a perfluoroalkyl group-containing alkoxysilane represented by the following general formula (I) is preferable.

[0027]

Embedded image R _f −X _p −Si (OR ² ) _m (R ¹ ) _3-m (I)

In the above general formula (I), R _f represents a perfluoroalkyl group, X represents a divalent linking group, and R ¹ and R ² each independently represent an alkyl group. p represents an integer of 1 to 4 and m represents an integer of 1 to 3.

In the above-mentioned perfluoroalkyl group (R _f ), the carbon number is usually 3 to 9, preferably 5 to 9, and more preferably 6 to 8. Examples of such a perfluoroalkyl group include a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, a perfluorooctyl group, a perfluorononyl group and the like.

Examples of the divalent linking group (X) include alkylene groups such as methylene group, ethylene group, propylene group and butylene group; arylene groups such as phenylene group and naphthylene group; -OC (O ) -NH-, -OR
³ - or -S-R ³ - group represented by (wherein R ³ represents an alkylene group), further, and a group to which they are bonded can be mentioned. Among these, an alkylene group, -OC (O)
A group represented by —NH—, —O—R ³ — or —S—R ³ — is preferable, and an alkylene group is particularly preferable. And in an alkylene group, a C2-C4 alkylene group is preferable and an ethylene group or a propylene group is especially preferable.

As R ¹ and R ² of the above alkyl group,
An alkyl group having 1 to 6 carbon atoms, preferably 1 carbon atom
~ 4 alkyl groups. As such an alkyl group,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. Of these, a methyl group is particularly preferable.

The above integer p is preferably 2 or 3, and more preferably 2. The integer m is preferably 2 or 3, and more preferably 3.

Specific examples of the fluorine-containing silane coupling agent (perfluoroalkyl group-containing alkoxysilane) represented by the general formula (I) include 1H, 1H, 2H, 2H.
-Perfluorohexyltrimethoxysilane, 1H, 1
H, 2H, 2H-perfluorohexyltriethoxysilane, 1H, 1H, 2H, 2H, 3H, 3H-perfluorohexyltrimethoxysilane, 1H, 1H, 2H, 2
H, 3H, 3H-perfluorohexyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2
H, 3H, 3H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H, 3H, 3H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2H
-Perfluorodecyltrimethoxysilane, 1H, 1H,
2H, 2H-perfluorodecyltriethoxysilane, 1
H, 1H, 2H, 2H, 3H, 3H-perfluorodecyltrimethoxysilane, 1H, 1H, 2H, 2H, 3H,
3H-perfluorodecyltriethoxysilane 1H, 1
H, 2H, 2H-perfluorohexyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H-perfluorohexyldiethoxymonoethylsilane, 1H, 1H, 2H,
2H, 3H, 3H-perfluorohexyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H, 3H, 3H-
Perfluorohexyldiethoxymonoethylsilane, 1
H, 1H, 2H, 2H-perfluorooctyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H-perfluorooctyldiethoxymonoethylsilane, 1H, 1H,
2H, 2H, 3H, 3H-perfluorooctyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H, 3H,
3H-perfluorooctyldiethoxymonoethylsilane, 1H, 1H, 2H, 2H-perfluorodecyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H-perfluorodecyldiethoxymonoethylsilane, 1H, 1
H, 2H, 2H, 3H, 3H-perfluorodecyldimethoxymonomethylsilane, 1H, 1H, 2H, 2H, 3
H, 3H-perfluorodecyldiethoxy monoethylsilane etc. are mentioned.

The fluorine-containing silane coupling agent represented by the above general formula (I) can be obtained, for example, by reacting a fluorine group-containing compound with an alkoxysilyl group-containing compound (silane coupling agent). .

Examples of the fluorine group-containing compound include hexafluoroisopropanol and 2 (perfluoro-n).
-Butyl) ethanol, 4,4,4 trifluoro 3,3
Dimethoxybutanol, dimethyl 2,2,2 trifluoropropionylcarbinol, 2 (perfluoro-n-
Hexyl) ethanol, 3, 3, 4, 4, 5, 5, 6,
6 octafluorooctane 1,8 diol, 3 (perfluoro-n-hexyl), one end is a perfluoroalkyl group similar to the above, the other end is an isocyanate group, a carboxyl group, an epoxy group, amino Base,
Examples thereof include compounds having a reactive double bond.

On the other hand, examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane, 2-
(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane,
Examples thereof include compounds containing an isocyanate group and having a terminal trialkoxysilane.

As the method of reacting the fluorine group-containing compound with the silane coupling agent, for example, for each compound having a double bond, a method of copolymerizing with a radical polymerization initiator, and a method of reacting with an epoxy group Reaction with amino groups or carboxyl groups, isocyanate groups and hydroxyl groups,
A known method utilizing a reaction with an amino group or a carboxyl group can be adopted.

Examples of the above-mentioned fluorine-containing surfactant include perfluoroalkyl oligomers having a perfluoroalkyl group, such as perfluoroalkylcarboxylic acid salts, perfluoroalkylphosphoric acid esters, perfluoroalkylammonium salts, and perfluxes. Examples thereof include all ethylene oxide adducts and perfluorocarboxylic acid salts. For example, "SC-101" and "SC-105" manufactured by Asahi Glass Co., Ltd. can be preferably used as the fluorine-containing surfactant.

As the fluororesin powder, for example, a tetrafluoroethylene polymer is preferably used, and its average molecular weight is usually 1,500 to 20,000, preferably 50.
The average particle size is usually 0.
It is 1 to 20 μm, preferably 0.1 to 1 μm.

The composition of the present invention may contain another hydrophobic compound in addition to the above-mentioned component B (fluorine-containing compound). Examples of other hydrophobic compounds include silicone resin powder and silicone-based surfactants. The average particle diameter of the silicone resin powder is usually 0.1 to 20 μm, preferably 0.1 to 1 μm. Examples of silicone-based surfactants include those having methylpolysiloxane as a hydrophobic group and polyalkylene oxide as a hydrophilic group. Specifically, "SILWET L-7001" manufactured by Nippon Unicar Co., Ltd. is preferably used.

The composition of the present invention preferably further contains a resin component compatible with the component A. Such a resin component functions as a matrix for the silicon component and the fluorine component. Examples of the resin component compatible with the component A include at least one selected from general resins such as acrylic resin, epoxy resin, saturated or unsaturated polyester resin, and polyurethane resin. The acrylic resin of is preferably used.

The acrylic resin in the present invention preferably contains at least one of a hydroxyl group and a silyl group. Furthermore, the acrylic resin may have one or more substituents such as an isocyanate group, an epoxy group, a carboxyl group, a dialkylaminoethyl group, an N-methylol (meth) acrylamide group, a phosphoric acid ester group, and a phosphorous acid ester group. It can be included.

The above-mentioned hydroxyl group or silyl group is
It can be used for a condensation reaction with a partial hydrolyzate of tetramethoxysilane, and the above-mentioned epoxy group, carboxyl group, dialkylaminoethyl group and the like have an effect of adhering to a base material and promoting a crosslinking reaction.

The acrylic resin can be obtained as a homopolymer or copolymer of various acrylic compounds (monomers). Examples of such a monomer include methacrylic acid, acrylic acid, or a mixture thereof, as well as various acrylic compounds described below.

For example, a compound (for example, glycidyl methacrylate, glycidyl acrylate, etc.) in which an alkyl group of alkyl (meth) acrylate (especially an alkyl group having 1 to 6 carbon atoms) is substituted with an epoxy group, methacrylic acid alkyl ester (for example, Methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, etc.), alkyl acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate,
Lauryl acrylate, etc.), hydroxy group-containing (meth) acrylic acid ester (eg, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc.), 2-
(Meth) acryloyloxyalkyl dicarboxylic acid esters (for example, 2- (meth) acryloyloxyethyl succinic acid monoester, 2- (meth) acryloyloxyethyl phthalic acid monoester, 2- (meth) acryloyloxy-2-hydroxy) Propylphthalic acid diester, etc.), dialkylaminoethyl (meth) acrylates (eg, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.), various allyl glycidyl ethers, mono (2-
Methacryloyloxy) acid phosphate, mono (2-acryloyloxy) acid phosphate and the like can be mentioned.

In the present invention, a silyl group-containing acrylic resin (copolymer) is particularly preferable, and a copolymer in which the silyl group is an organooxysilyl group is particularly preferable.

The silyl group-containing acrylic resin as described above is
It can be produced by copolymerizing the following monomers (1) to (4).

(1) Vinyl group-containing alkoxysilane (2) Vinyl group-containing polysiloxane (3) Hydroxyl group-containing methacrylic acid ester and / or acrylic acid ester (4) Methacrylic acid ester and / or acrylic acid ester

In particular, in order to impart the best coating physical properties to the composition of the present invention, the ratio of the above compounds (1) to (4) to be used in the production of the copolymer is 0.1% vinyl group-containing alkoxysilane. To 20% by weight, vinyl group-containing polysiloxane 0.1 to 20% by weight, hydroxyl group-containing methacrylic acid ester and / or acrylic acid ester 10 to 30% by weight, methacrylic acid ester and / or acrylic acid ester 40 to 80% by weight Is preferred.

Specific examples of the above (3) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, glycerol acrylate and acrylic. Acid 2-hydroxy-3-phenyloxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxypentyl methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, methacrylic acid methacrylate Examples thereof include glycerol acid.

In the above (4), the ester group preferably has 1 to 12 carbon atoms. Then, as specific examples thereof, methyl acrylate, ethyl acrylate, butyl acrylate, allyl acrylate, phenyl acrylate, methyl methacrylate, butyl methacrylate, pentyl methacrylate, lauryl methacrylate, vinyl methacrylate,
Allyl methacrylate, 2-ethylhexyl acrylate,
Examples thereof include octyl acrylate, lauryl acrylate, stearyl acrylate, ethyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate and the like.

In the copolymerization of the above-mentioned monomers (1) to (4), it is preferable to use an organic acid having 3 or more carbon atoms mixed with the monomer. The ratio to the total amount of organic acid is 0.1 to 5% by weight. Further, a radical initiator such as benzoyl peroxide or azobisisobutyronitrile is used as a polymerization catalyst, and the ratio of its use is usually 0.1% as a ratio to the total amount of all monomers.
It is 1 to 3% by weight, preferably 0.2 to 2% by weight.

The copolymerization may be either bulk polymerization or solution polymerization, but solution polymerization is most preferable in the compounding step for coating. Examples of the organic solvent used in the solution polymerization include alcohols, and specific examples thereof include methanol, ethanol, isopropyl alcohol, n-butanol, isoamyl alcohol, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. In addition, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone may be used. The production (copolymerization) of the acrylic resin is usually carried out under the conditions of 60 to 150 ° C. for 2 to 10 hours, and the molecular weight of the acrylic resin is 3,000 to
It is preferably 300,000.

A solvent (or a dispersion medium) is usually added to the composition of the present invention in order to impart a film-forming property in which the composition is rapidly cured in the field (at room temperature). Examples of such a solvent include alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers and the like.

Examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, and octanol. Examples of glycol derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n. -Propyl ether, ethylene glycol mono-n-butyl ether and the like.

Hydrocarbons include benzene, kerosene, toluene, xylene, etc., esters include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc., and ketones , Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like, and examples of the ethers include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan, tetrahydrofuran and the like.

In the present invention, for example, a water-surfactant type dispersion medium may be used. As the surfactant, anionic, cationic or nonionic surfactant is generally used.

Examples of the anionic surfactant include carboxylic acid salts, sulfonic acid salts, sulfuric acid ester salts, phosphoric acid ester salts, and the like.
To organic acid or inorganic acid salts of tertiary amines, quaternary ammonium salts, polyoxyethylene alkylamine salts, and the like, and nonionic surfactants include sorbitan dialkyl esters and ethylene glycol condensates of sorbitan alkyl esters, Examples thereof include aliphatic alcohol polyethylene glycol condensate, alkylphenol polyethylene glycol condensate, polypropylene glycol polyethylene glycol condensate, and the like. These surfactants are usually contained in the dispersion medium of water-surfactant system in an amount of 0.1 to 5% by weight. The dispersion (emulsification) can be performed by a known method such as homomixer, colloid mill and ultrasonic wave using an appropriate amount of water.

The greatest feature of the composition containing a silicon component and a fluorine component of the present invention is that when it is formed into a coating film or a film,
The surface free energy (γ) at 25 ° C. of the surface is 5 to 24 [mN / m], and the ratio (γ ^d /) of the dispersive force component (γ ^d ) and the non-dispersive force component (γ ^p ) in the surface free energy. γ ^p ) is 8.5 to 20, and the increase rate of the surface free energy before and after the immersion treatment of this coating film or film at 90 ° C. for 5 minutes is within 1.5 times.

In the present invention, the surface free energy of the coating film or film is the surface free energy (γ) on the solid, which is obtained as follows.

The surface free energy can be considered to consist of a dispersive force component (γ ^d ) and a non-dispersive force component (γ ^p ) based on the van der Waals force, as shown in the following equation (1). Then, this equation gives the surface free energies (γ _S , γ _L ,
γ _SL ) also applies. Therefore, the following Young's equation (Equation (2)) and Fowkes's equation (Equation (3)) are applied to determine the surface free energy (γ _S ) on the solid as the contact angle of the droplet and the surface free energy on the droplet. The formula (4) represented by energy (γ _L ) is derived.

The Young's equation is that for a liquid (droplet) in equilibrium with the solid on the surface of the solid,
It is an equation showing the relationship between each surface free energy at the liquid / interface and the contact angle formed by the droplet. Also, Fowkes
Is a formula showing that the free energy at the interface is the amount obtained by reducing the free energy by the interaction component (geometric average amount) corresponding to each component in solid and liquid.

[0063]

Γ = γ ^d + γ ^p (1) γ _S = γ _L cos θ + γ _SL (2) γ _SL = γ _S + γ _L -2 (γ _S ^d γ _L ^d ) ^1/2 -2 (γ _S ^P γ _L ^P ) ^1/2 (3) γ _L (1 + cos θ) = 2 (γ _S ^d γ _L ^d ) ^1/2 +2 (γ _S ^P γ _L ^P ) ^1/2 (4)

However, the meanings of the symbols in the above equations (1) to (4) are as follows.

[0065]

[Table 1] γ ^d : Dispersion force component γ ^p : Non-dispersion force component γ _S : Surface free energy on solid γ _L : Surface free energy on droplet γ _SL : Free energy at solid-liquid interface γ _S ^d : Solid Dispersion force component on the surface free energy on γ _S ^P : Non-dispersion force component on the surface free energy on solid γ _L ^d : Dispersion force component on the surface free energy on droplet γ _S ^P : On the surface free energy on solid Non-dispersive force component

Here, 2 which constitutes the surface free energy
The components (γ ^d , γ ^p ) are obtained from two or more types of test solutions, and these two values are substituted into equation (4) to obtain each surface free energy (γ _S , γ _L , γ _SL ) as a simultaneous equation. To be
Specifically, two or more kinds of reagent solutions having known γ _L ^d and γ _L ^P may be used.

A method using water and n-decane as a test solution will be described below. The surface free energy (γ _L ) of water is 72.8 [mN / m], and when this is divided into (γ _L ^d ) and (γ _L ^P ), γ _L ^d = 21.8, and γ _L ^P = 51. Also, that of n-decane is γ _L =
23.9 [mN / m], which is divided into (γ _L ^d ) and (γ _L ^P ), γ _L ^d = 23.9 [mN / m], and γ _L ^P = 0 [mN / m].

The contact angle with the solid surface is measured using a test solution having only a dispersive force such as n-decane. At this time, since there is no non-dispersive force component (γ ^P = 0), from equation (1), γ _L =
γ _L ^d + γ _L ^P = γ _L ^d . Then, the equation (4) becomes the following equation (4-1), from which the equation (4-2) is derived.

[0069]

## EQU2 ## γ _L (1 + cos θ) = 2 (γ _S ^d γ _L ^d ) ^1/2 (4-1) cos θ = -1 + 2 (γ _S ^d / γ _L ^d ) ^1/2 (4-2)

Then, the contact angle was measured, and from the plot of cos θ and γ _L ^{d in} equation (4-2), the slope (γ
_S ^d ) is obtained. Next, by substituting the value of γ _S ^{d into} equation (4) for water, substituting the contact angles of water, γ _L , γ _L ^d , and γ _L ^P for γ _S ^P
Ask for. As a result, γ _S ^d + γ _S ^P is obtained as the surface free energy (γ _S ) on the solid.

By satisfying the above conditions, the composition of the present invention exhibits an effect of preventing snow accretion in a wide temperature range such as -10 ° C to -0.1 ° C. Such an effect is a surprising effect that cannot be obtained by the conventional composition.

That is, when the surface free energy (γ) at 25 ° C. is less than 5 mN / m, it becomes difficult to form a water film and the snow sliding property deteriorates. Is reduced. The surface free energy (γ) is preferably 6 to 22 mN / m, more preferably 7 to 20 mN / m, and particularly preferably 8 to 18 mN / m.
m. Further, the ratio (γ ^d ) between the dispersive force component (γ ^d ) and the non-dispersive force component (γ ^p ) of the surface free energy (γ) described above.
When / γ ^p ) is less than 8.5, it becomes difficult to form a water film, and the snow sliding property deteriorates. The above ratio (γ ^d / γ ^p ) is preferably 9 or more, more preferably 12 or more, and the upper limit thereof is usually 20.

The composition of the present invention in which the surface of the coating film or film satisfies the above-mentioned conditions is prepared by uniformly mixing the above-mentioned components A and B. At this time, the amount of the component B is usually 0.1 to 100 parts by weight, preferably 1 to 100 parts by weight (however, converted to SiO ₂ ).
It is mixed in a ratio of 50 parts by weight. B component ratio is 0.1
If the amount is less than 100 parts by weight, the effect of preventing snow accretion is low and 100
If the amount is more than parts by weight, the strength of the coating film and the adhesion to the base material are reduced.

When the above acrylic resin is used, its proportion is usually 20 to 2,000 parts by weight, preferably 30 to 1,000 parts by weight, based on 100 parts by weight of silicon atom (provided that it is converted into SiO ₂ ). And more preferably 50 to 400 parts by weight. If the amount of the acrylic resin is small, there is a risk of cracking in the coating film after film formation, and if too large, scratch resistance, acid rain resistance,
Poor stain resistance.

When the above-mentioned solvent or dispersion medium is used, the ratio of use is determined in consideration of the concentration of silicon atoms (converted to SiO ₂ ) in the entire composition. That is,
The concentration of silicon atoms (converted to SiO ₂ ) in all compositions is
It is usually 0.05% by weight or more, preferably 0.1% by weight or more. When the concentration of silicon atoms is less than 0.05% by weight, the snow sliding property and the effect of preventing snow accretion are poorly expressed. Usually, the upper limit of the concentration of silicon atoms is 20% by weight.

In the present invention, a composition containing water and a solvent such as alcohol is recommended. The addition of water has the effect of hydrolyzing the above-mentioned component A (Si (OR) ₄ etc.) to form a silanol group, thereby enhancing the hydrophilic effect. The mixing ratio of each component is as follows. That is, the above A
Water is usually 1 to 100 parts by weight, preferably 10 to 50 parts by weight, and a solvent such as alcohol is usually 100 to 5,000 parts by weight, preferably 500 to 100 parts by weight of the components.
~ 2,000 parts by weight.

When the composition of the present invention is formed into a coating film or film, the above-mentioned components A and B are compatible with each other on the surface and are dispersed uniformly. Therefore, the composition of the present invention is
When exposed to the outdoors and repeatedly contacted and rubbed with snow and ice, the above components do not drop out, wear, or decrease, and the effect is highly durable.

The composition of the present invention is applied to various base materials and used as a snow / ice preventing member. Examples of the base material include roofs, electric wires, electric power towers, road signs, ships, aircraft fuselages, wings, automobiles and train vehicles, glass, solar panels, and outdoor products having a resin coating film. Further, the composition of the present invention can be applied to any material such as metal, glass, organic coating film, resin molded product, various laminated bodies (composites), and particularly, as a laminated body, a synthetic resin sheet is used. A composite body in which metal sheets are laminated on both sides of (for example, a product name “Alpolic” manufactured by Mitsubishi Chemical Industrial Co., Ltd.) is preferably used.

[0079]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the following examples, the reagents used are as follows.

(1) Component A: polymethoxypolysiloxane which is a partial hydrolysis-condensation product of tetramethoxysilane (“MKC silicate MS51” manufactured by Mitsubishi Chemical Corporation)

(2) Component B: Fluorine-containing silane coupling agent ("KBM7803" manufactured by Shin-Etsu Chemical Co., Ltd .: heptadecafluorodecyltrimethoxysilane) or fluorine-containing surfactant ("Surflon SC" manufactured by Asahi Glass Co., Ltd.). −
101 ")

(3) Acrylic resin: Methacrylic acid ester copolymer ("A-52-40" manufactured by Showa Highpolymer Co., Ltd.) Acrylic copolymer (C-6 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
880 ”) Silicone modified acrylic resin (“ CT ”manufactured by Chisso Corporation)
-8101 ")

(4) Mixed solvent (A): industrial ethanol 33.2 parts by weight, propylene glycol monomethyl ether acetate 34.0 parts by weight, xylene 13.3 parts by weight, propylene glycol monomethyl ether 13.3
Parts by weight, isopropyl alcohol 6.2 parts by weight (total 1
00.0 parts by weight)

(5) Mixed solvent (B): industrial methanol 33.0 parts by weight, methyl acetoacetate 34.0 parts by weight, methyl isobutyl ketone 13.0 parts by weight, propylene glycol monomethyl ether 13.0 parts by weight, isopropyl Mixed solvent consisting of 7.0 parts by weight of alcohol (total 100.0 parts by weight)

(6) Organic metal catalyst: acetylacetone aluminum

Further, the actual exposure test method in the following examples is as follows.

<Test Method for Exposure to Natural Snow> The test coating film was set on the exposure table in the Hokkaido Industrial Testing Laboratory at an angle of 45 ° from the horizontal, and the extent of the amount of snow covered on the test coating film ( The area ratio) was visually observed, and evaluation was made on an 11-point scale, with "0" for no snow and "10" for total snow cover.

<Exposure test method for artificial snow> The test coating film was placed on the exposure table in the artificial snowfall chamber at an angle of 45 ° from the horizontal, and the artificial snowfall machine was used to set the temperature to -10 ° C (coating surface temperature). In the condition of a snowfall rate of 2.5 cm / hr, snow equivalent to fresh snow (density of 0.15 g / ml) was dropped, and the extent of the amount of snow covered on the test coating (area ratio of snow covered) was visually observed and no snow was found. "0" in case of, and "10" in case of total snow cover
It was evaluated in 11 steps.

Example 1 45.2 parts by weight of mixed solvent (A), 3.4 parts by weight of polymethoxypolysiloxane, 1.0 part by weight of deionized water, and 0.3 parts by weight of organometallic catalyst were stirred at room temperature. And mixed well, and aged at 65 ° C. for 2 hours. Then, after cooling to 40 ° C., 45.2 parts by weight of the mixed solvent (A), 0.5 parts by weight of a fluorine-containing silane coupling agent, and 3.6 parts by weight of a methacrylic acid ester copolymer are sequentially added to the coating solution. (1)
Got Next, the coating liquid (1) was uniformly applied to an aluminum plate so that the dry thickness was 2 μm, and dried at room temperature for 7 days to be cured. Then, from February 24, 2001 to March 8, 2001, an exposure test for natural snow was conducted.

Table 2 shows the values of the surface free energy (γ) of the coating film and the ratio (γ ^d / γ ^p ) of the dispersive force component (γ ^d ) and the non-dispersive force component (γ ^p ). The result of the exposure test to natural snow is shown. The components of the surface free energy (γ) of the coating film were calculated from the contact angles of water, ethylene glycol (EG) and n-decane (DE) shown in Table 2.

Comparative Example 1 In Example 1, instead of 0.5 part by weight of the fluorine-containing silane coupling agent, a fluorine-containing surfactant 1.6 was used.
A coating liquid (2) was obtained in the same manner as in Example 1 except that 7 parts by weight was used. Then, an exposure test for natural snow was conducted in the same manner as in Example 1. Table 2 shows the values of the surface free energy (γ) of the coating film and the ratio (γ ^d / γ ^p ) of the dispersive force component (γ ^d ) and the non-dispersive force component (γ ^p ). The results of the exposure test are shown.

[0092]

[Table 2]

[0093]

[Table 3]

From the results of the exposure test on natural snow, the following was considered. That is, Example 1 was clearly superior in the effect of preventing snow accretion at around -7 ° C, and the test plate was excellent in the effect of preventing snow accretion without snowfall even during snowfall. on the other hand,
Regarding the snow sliding performance at around -3 ° C, no significant difference was observed between the example and the comparative example. From the above, it can be seen that when the composition of the present invention is used, it also has snow sliding properties, can prevent snow accretion during snowfall, and can achieve both snow sliding properties and snow accretion prevention properties.

Examples 2 to 7 56.68 parts by weight of the mixed solvent (B), 30.77 parts by weight of polymethoxypolysiloxane, and 6.15 parts by weight of a solution of an organometallic catalyst in methanol (concentration: 5% by weight) at room temperature. Stir to mix well. Next, 6.5 parts by weight of ion-exchanged water was added and stirred for 5 minutes, and then the stirring was continued at 60 ° C. for 2 hours. Then, the acrylic resin shown in Table 4 was added in the amount shown in the same table, and stirring was continued at 60 ° C. for 2 hours. Then, the fluorine-containing compound shown in Table 4 was added in the amount shown in the same table, and 6
Stirring was continued at 0 ° C. for 2 hours. Then, after cooling to room temperature, the amount of mixed solvent (B) (for dilution) shown in Table 4 was added to obtain a coating liquid. Next, the coating liquid was uniformly applied to the aluminum plate so that the dry thickness was 2 μm, and dried at room temperature for 7 days to be cured. Then, an exposure test on artificial snow was conducted. Further, in order to evaluate the weather resistance of the coating film, the measurement of the surface free energy relationship of the coating film was also performed on the coating film after hot water treatment (immersing in warm water at 90 ° C. for 5 minutes). Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

Example 8 A coating solution was prepared in the same manner as in Example 2 except that the reagents shown in Table 5 were used in the amounts shown in Table 5, and the exposure test to artificial snow was conducted. It was Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

Example 9 A coating solution was prepared in the same manner as in Example 2 except that the order of addition of the acrylic resin and the fluorine-containing compound was reversed, and an exposure test for artificial snow was conducted. Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

Examples 10 to 12 In Example 2, the amount of the fluorine-containing surfactant shown in Table 5 was added after the addition of the diluting mixed solvent (B), and the mixture was stirred at room temperature for 1 hour.
A coating solution was obtained in the same manner as in Example 2 except that the mixture was stirred for an hour, and an exposure test for artificial snow and the like were performed. However,
In Examples 11 and 12, the amounts of the fluorine-containing silane coupling agent and the diluting mixed solvent (B) used were changed as shown in Table 5. Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

[0099]

[Table 4]

[0100]

[Table 5]

Comparative Example 2 Comprising a fluororesin main agent and an isocyanate curing agent 2
Liquid hardening type resin paint (V Freon # manufactured by Dainippon Paint Co., Ltd.)
100) was mixed so that the weight ratio of the main component and the curing agent was 4: 1 to obtain a resin coating material. This is applied to an aluminum plate, dried overnight at room temperature, and then cured at 50 ° C. for 5 hours, 4
Hydrophilization was performed overnight at 0 ° C. × 95 RH% to obtain a coating film. Then, in the same manner as in Example 2, an exposure test for artificial snow was performed. Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

Comparative Example 3 A coating film was prepared in the same manner as in Comparative Example 2 except that 5% by weight of a silicate oligomer (MKC Silicate MS51 manufactured by Mitsubishi Chemical Corporation) was added to the resin coating obtained in the same manner as in Comparative Example 2. It was obtained and tested. Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

Comparative Example 4 A coating film was prepared in the same manner as in Comparative Example 2 except that 10% by weight of a silicate oligomer (MKC Silicate MS51 manufactured by Mitsubishi Chemical Corporation) was added to the resin coating obtained in the same manner as in Comparative Example 2. It was obtained and tested. Table 6 shows the results of the exposure test to artificial snow and the measurement results of the surface free energy relationship of the coating film before and after hot water treatment.

[0104]

[Table 6]

The composition of the present invention has a γ ^d / γ even after the hot water test.
It can be seen that the value of ^P is 8.5 or more and the increment is within 1.5 times. This indicates that the composition of the present invention can maintain excellent weather resistance even after its surface is exposed to severe conditions.

[0106]

EFFECTS OF THE INVENTION The present invention provides a composition having both the effect of preventing snow accretion during snowfall and low temperature and the snow sliding performance at the time of temperature rise, and the industrial value of the present invention is remarkable.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/04 C09D 183/04 183/08 183/08 (72) Inventor Takeshi Sawai Hachiman Nishi Ward, Kitakyushu City, Fukuoka Prefecture Kurosaki Shiroishi No. 1 Mitsubishi Chemical Co., Ltd. (72) Inventor Seiichiro Tanaka No. 1 Kurosaki Shiroishi No. 1 Yachiman Nishi-ku, Kitakyushu, Fukuoka Prefecture F Term (reference) 4J002 BG03X CP02W EX026 EX036 FD310 GL00 4J038 CL002 DL021 DL031 DL072 DL102 NA05 PB05 PB07

Claims (7)

[Claims] 1. At least component A and B defined below:
Silicon for a coating or film containing a component and, if necessary, a silicon-containing compound other than the component A in a ratio of 25 parts by weight or less with respect to 100 parts by weight of the component A (provided that it is converted into SiO ₂ ). 25% of the surface of a composition containing a component and a fluorine component when formed into a coating film or film.
Surface free energy (γ) at ℃ 5 to 24 [mN
/ M], and the ratio (γ ^d / γ ^p ) of the dispersive force component (γ ^d ) and the non-dispersive force component (γ ^p ) in the surface free energy
Is 8.5 to 20 and this coating film or film is 90
A composition containing a silicon component and a fluorine component, wherein the rate of increase in surface free energy before and after the immersion treatment at 5 ° C. for 5 minutes is within 1.5 times. <Component A>: Tetraalkoxysilane (a1), its partial hydrolysis-condensation product (a2), tetraalkoxysilane and / or its hydrolysis hydrolysis-condensation product obtained by adding more water than the theoretical amount of water to the partial hydrolysis-condensation product ( one or more compounds selected from the group a3) <component B>: fluorine-containing compound 2. The composition according to claim 1, wherein the fluorine-containing compound is a fluorine-containing silane coupling agent or a fluorine-containing surfactant. 3. The composition according to claim 2, wherein the fluorine-containing silane coupling agent is a perfluoroalkyl group-containing alkoxysilane represented by the following general formula (I). Embedded image R _f —X _p —Si (OR ² ) _m (R ¹ ) _3-m (I) (In the general formula (I), R _f represents a perfluoroalkyl group, and X represents a divalent bond. Group, R ¹ and R ² each independently represent an alkyl group, p represents an integer of 1 to 4, and m represents 1
Represents an integer of 3; ) 4. The composition according to claim 1, further comprising a resin component compatible with the component A. 5. The composition according to claim 4, wherein the resin component is a silyl group-containing acrylic resin. 6. The composition according to claim 5, wherein the silyl group is an organoxysilyl group. 7. A snow-ice prevention member, the surface of which is formed of the composition according to any one of claims 1 to 6.