JP2000239601A - Polymer composition capable of forming water-slip surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer composition capable of forming an exceedingly water-repellent surface from which adherent water drops can easily slip by including a hydrolyzable-alkoxysilyl-containing siloxane polymer obtained by the copolymerization of a siloxane macromonomer having a specified structure with a hydrolyzable-alkoxysilyl-containing monomer and other copolymerizable unsaturated monomers. SOLUTION: This composition is one containing a hydrolyzable-alkoxysilyl- containing siloxane polymer having a number-average molecular weight of 1,000-100,000 and obtained by copolymerizing 1-40 wt.% siloxane macromonomer represented by formula I or II with 5-50 wt.% hydrolyzable-alkoxysilyl-containing monomer such as vinyltrimethoxysilane and 10-94 wt.% other copolymerizable unsaturated monomers such as (meth)acrylic acid. The composition may additionally contain a crosslinking agent such as an amino resin, a curing catalyst, a solvent, etc. In the formulae, R1 is a 1-10C alkyl; R2, R5 and R6 are each a divalent 1-10C hydrocarbon group; R3, R4 and R7 are each hydrogen or methyl; and m and n are each 6-300.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a water-resistant,
Further, the present invention relates to a polymer composition capable of forming a superhydrophobic surface on which attached water droplets can easily slide.

[0002]

2. Description of the Related Art Conventionally, in order to make the surface of an object less wet, that is, to impart water repellency to the surface of the object, the surface of the object is made of, for example, a silicon compound or resin, a fluorine resin, a polyolefin resin, or the like. Coating with a hydrophobic material has been performed. When water adheres to the surface of the object subjected to the surface hydrophobization treatment in this way, the water is repelled to form spherical water droplets, and large water droplets fall by their own weight, while small water droplets remain strongly adhered to the object surface. There is often a phenomenon that the attachment surface does not fall even if it is inclined vertically. In such a case, a dry surface without water droplets cannot be obtained unless the water droplets are forcibly removed by a mechanical method such as wiping off water droplets.

[0003] For this reason, various studies have been made on the development of highly hydrophobic materials for rolling adhered water droplets as close as possible to spheres and rolling off the object surface by increasing the contact angle with water by increasing the hydrophobicity of the object surface as much as possible. Is being done. Further, a physical method for forming a roughened surface or a hairy projection on the surface has been studied. However, the materials proposed so far to increase the contact angle with water have problems such as poor mechanical properties such as hardness and strength, and difficulty in production of special materials. Further, physical methods such as surface roughening and formation of hairy projections have a problem that the effect is weakened if the object surface is rubbed once.

[0004] Therefore, there is a strong demand for a coating material which can impart water repellency to the surface of an object and at the same time easily remove attached water droplets from the surface of the object, and further has a water-sliding durability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to impart water repellency to the surface of an object, and at the same time, easily remove attached water droplets from the surface of the object. An object of the present invention is to provide a coating material having water sustainability.

[0006]

Means for Solving the Problems The present inventors have solved the above problems and provided water repellency to the surface of an object,
Intensive investigations have been made to develop a material that can easily remove the attached water droplets from the surface of the object and have a continuous water slide.

As a result, they have found that a film formed from a specific hydrolyzable alkoxysilyl group-containing siloxane polymer meets the above-mentioned object, and have completed the present invention.

[0008] Thus, according to the present invention, the expression (a)

[0009]

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In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms; R ² represents a divalent hydrocarbon group having 1 to 6 carbon atoms; R ³ represents a hydrogen atom or a methyl group; Is 6 ~
Is a number of 300 and / or

[0011]

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In the formula, R ⁴ and R ⁷ are the same or different and represent a hydrogen atom or a methyl group; R ⁵ and R ⁶ are the same or different and represent a divalent hydrocarbon group having 1 to 6 carbon atoms; Is 6
1 to 40% by weight of a siloxane macromonomer represented by the following formula: (b) 5 to 50% by weight of a monomer containing a hydrolyzable alkoxysilyl group, and (c) other unsaturated copolymerizable therewith. There is provided a polymer composition capable of forming a water-slidable surface, characterized by containing a hydrolyzable alkoxysilyl group-containing siloxane polymer (A) obtained by copolymerization of 10 to 94% by weight of a monomer as an essential component.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polymer composition of the present invention will be described in more detail.

Siloxane Macromonomer (a) In the present invention, the siloxane macromonomer (a) used for producing the hydrolyzable alkoxysilyl group-containing siloxane polymer (A) is one that imparts water-sliding property to the surface of a crosslinked coating film. And the following equation

[0015]

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And / or

[0017]

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Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is an alkyl group having 1 to 10 carbon atoms.
6, a divalent hydrocarbon group, R ³ represents a hydrogen atom or a methyl group, R ⁴ and R ⁷ are the same or different and represent a hydrogen atom or a methyl group, and R ⁵ and R ⁶ are the same or different Represents a divalent hydrocarbon group having 1 to 6 carbon atoms;
And n mean the average degree of polymerization of dimethylsiloxane units, and both are numbers in the range of 6 to 300, preferably 6 to 100.

The siloxane macromonomer (a) is generally used in an amount of 300 to 30,000, preferably 500 to 20,000.
It can have a number average molecular weight in the range of 00.

Hydrolyzable alkoxysilyl group-containing monomer
-(B) In the present invention, the hydrolyzable alkoxysilyl group-containing monomer (b) used in the production of the hydrolyzable alkoxysilyl group-containing siloxane polymer (A) has a polymerizable double bond and a hydrolyzable alkoxysilyl group in one molecule. A compound having a decomposable alkoxysilyl group, specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, vinyl Examples thereof include triacetoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, and γ- (meth) acryloyloxypropyltriethoxysilane.

Other unsaturated monomers (c) Examples of other unsaturated monomers (c) copolymerized with the siloxane macromonomer (a) and the hydrolyzable alkoxysilyl group-containing monomer (b) include, for example, acrylic Carboxyl group-containing unsaturated acids such as acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate Monomer: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, or other acrylic acid or methacrylic acid having 2 to 2 carbon atoms
Hydroxyalkyl esters of 8; monoesters of polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol with unsaturated carboxylic acids such as (meth) acrylic acid; hydroxyalkyl vinyl ethers, allyl alcohol and (meth) acrylic acid Adducts of hydroxyalkyl esters, (poly) alkylene glycol mono (meth) acrylates, and the like with lactones (eg, ε-caprolactone, γ-valerolactone); polyether polyols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; Monoether with a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth) acrylate; α, β-unsaturated carboxylic acid, and Kadura E10 (Shell Chemical Co., Ltd.) ) Adducts of monoepoxy compounds such as and α- olefin epoxide; glycidyl (meth) acrylate and acetic acid, propionic acid, p-t-
Adducts with monobasic acids such as butylbenzoic acid and fatty acids; unsaturated compounds containing acid anhydride groups such as maleic anhydride and itaconic anhydride; and ethylene glycol, 1,6-hexanediol, neopentyl glycol, etc. Monoesters or diesters with glycols; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; chlorine-containing hydroxyl-containing monomers such as 3-chloro-2-hydroxypropyl (meth) acrylate; allyl alcohol; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
Butyl (meth) acrylate (n-, i-, t-), hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, (Meth) lauryl acrylate,
C1-18 alkyl or cycloalkyl esters of acrylic acid or methacrylic acid, such as (meth) stearyl acrylate, cyclohexyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, Acrylic acid such as ethoxybutyl (meth) acrylate or methacrylic acid has 2 to 18 carbon atoms.
Chain alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether and octyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether Aryl vinyl ethers such as phenyl vinyl ether and trivinyl phenyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether; vinyl acetate, vinyl propionate, vinyl lactate and butyric acid Vinyl, vinyl isobutyrate, bicarbonate , Vinyl esters such as vinyl isocaproate, vinyl pivalate, vinyl caprate, and veova monomer (manufactured by Shell Chemical Co., Ltd.); propenyl esters such as isopropenyl acetate and isopropenyl propionate; ethylene, propylene, butylene, and vinyl chloride; Olefinic compound; styrene, α-methylstyrene,
Vinyl aromatic compounds such as vinyltoluene and α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, etc. Nitrogen-containing alkyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N
-Methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N -Dimethylaminoethyl (meth)
Polymerizable amides such as acrylamide; aromatic nitrogen-containing monomers such as 2-vinylpyridine, 1-vinyl-2-pyrrolidone and 4-vinylpyridine; polymerizable nitriles such as acrylonitrile and methacrylonitrile; glycidyl (meth) acrylate; Polymerizable glycidyl compounds such as allyl glycidyl ether; allyl monomers such as diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, pentaerythritol diallyl ether, and allyl glycidyl ether; perfluorobutylethyl (meth) Acrylate, perfluoroisononylethyl (meth) acryle
And perfluoroalkyl (meth) acrylates such as perfluorooctylethyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. A) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol diacrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, hydroxypropyl isocyanurate tri (meth) acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate,
Glycerol allyloxydi (meth) acrylate, 1,
1,1-tris (hydroxymethyl) ethanedi (meth)
Acrylate, 1,1,1-tris (hydroxymethyl) ethanetri (meth) acrylate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, diallyl isophthalate, pentaerythritol diallyl ether, divinylbenzene (Meth) acrylic acid esters of polyhydric alcohols such as

Hydroxy-containing alkoxysilyl group-containing siloxy
Sun Polymer (A) In the present invention, the hydrolyzable alkoxysilyl group-containing siloxane polymer (A) is the above-mentioned siloxane macromonomer (a), hydrolyzable alkoxysilyl group-containing vinyl monomer (b), and copolymerizable therewith. Can be obtained by copolymerization of another unsaturated monomer (c).

The copolymerization ratio of the siloxane macromonomer, the hydrolyzable alkoxysilyl group-containing vinyl monomer and, if necessary, other unsaturated monomers copolymerizable therewith is determined by the amount of the hydrolyzable alkoxysilyl group-containing siloxane polymer (A) obtained. Although it can be varied over a wide range depending on the physical properties desired for the above, it is generally desirable to be within the following range based on the total amount of the above monomers.

Siloxane macromonomer (a): 1-4
0% by weight, especially 2 to 25% by weight Hydrolyzable alkoxysilyl group-containing vinyl monomer (b): 5 to 50% by weight, especially 10 to 40% by weight Other unsaturated monomer (c): 10 to 94% by weight, Especially 3
The copolymerization of the above monomers is usually carried out in an organic solvent in the presence of about 0.01 to about 8 parts by weight of a polymerization initiator per 100 parts by weight of the total amount of the monomers at about -20 ° C. The reaction can be carried out at a temperature of from about 150 ° C. under normal pressure or optionally under a pressure of up to about 30 kg / cm ² G.

The hydrolyzable alkoxysilyl group-containing siloxane polymer (A) thus obtained is generally 1,0
00 to 100,000, preferably 3,000 to 50,
It may have a number average molecular weight in the range of 000.

In the present invention, a crosslinking agent (B) may be further contained.

As the crosslinking agent (B), an amino resin or an optionally blocked polyisocyanate compound is used.

As the amino resin, the melamine having 1 to 5 triazine rings or a condensate thereof having a molecular weight of 300 to 3,000, particularly 500 to 2,000 is preferred.
Partially or completely methylolated melamine resin in the range of, or further a part or all of the methylol group of a monohydric alcohol having 1 to 8 carbon atoms, for example,
Methylol melamine resins partially etherified or completely alkyl etherified with methanol, ethanol, propanol, butanol or the like can be used.

Examples of the above polyisocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, bis (isocyanatomethyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate and diphenylmethane. Aromatic, cycloaliphatic or aliphatic polyisocyanate compounds such as diisocyanate, and excessive amounts of these polyisocyanate compounds contain low-molecular-weight active hydrogen such as ethylene glycol, propylene glycol, trimethylolpropane, hexanetriol, and castor oil. Examples include isocyanate-terminated prepolymers obtained by reacting compounds.

These polyisocyanate compounds may be used as they are, or, if necessary, in a form in which isocyanate groups are blocked by a blocking agent.

Examples of the isocyanate blocking agent include phenols such as phenol, m-cresol, xylenol and thiophenol; methanol, ethanol, butanol, 2-ethylhexanol, cyclohexanol,
Alcohols such as ethylene glycol monomethyl ether; active hydrogen-containing compounds such as caprolactam, ethyl acetoacetate and diethyl malonate;
The blocking of the polyisocyanate compound using these blocking agents can be performed according to a method known per se.

In the present invention, the curing catalyst (C)
Can be contained.

As the curing catalyst (C), a self-condensation catalyst of a hydrolyzable alkoxysilyl group, a catalyst for a reaction between a hydroxyl group and an isocyanate, and a catalyst for a reaction between a hydroxyl group and an amino resin are used.

The self-condensing catalyst for the hydrolyzable alkoxysilyl group includes, for example, dibutyltin oxide,
Tin compounds such as monobutyltin hydrooxide, stannous chloride and tin oleate; chelate compounds such as aluminum chelate, titanium chelate and zirconium chelate; basic substances such as tetramethylammonium acetate and diazabicycloundecene; , Phosphoric acid, paratoluenesulfonic acid, trichloroacetic acid, trifluoromethanesulfonic acid, acidic substances such as monobutyl phosphate, dibutyl phosphate, and boron trifluoride.

Examples of the catalyst for the reaction between the hydroxyl group and the isocyanate include bismuth nitrate, lead 2-ethylhexanoate, lead benzoate, lead oleate, sodium trichlorophenolate, sodium propionate, lithium acetate and potassium oleate. , Tetrabutyltin,
Tributyltin chloride, dibutyltin dichloride, butyltin trichloride, tin chloride, tributyltin-o-phenolate, tributyltin cyanate, tin octylate, tin oleate, tin tartrate, dibutyltin di (2-ethylhexylate), dibenzyltin di (2- Ethylhexylate), dibutyltin dilaurate, dibutyltin diisooctyl maleate, dibutyltin sulfide, dibutyltin dibutoxide, dibutyltin bis (o-phenylphenolate), dibutyltin bis (acetylacetonate), di (2-ethylhexyl) tin oxide,
Titanium tetrachloride, dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride, iron trichloride, iron (III) 2-ethylhexanoate, iron acetylacetone (II)
I), ferrocene, antimony trichloride, antimony pentachloride, triphenylantimony dichloride, tolphenylantimony, uranium nitrate, cadmium nitrate, cadmium diethyldithiophosphate, cobalt benzoate, cobalt 2-ethylhexanoate, thorium nitrate, triphenyl Aluminum, trioctyl aluminum, aluminum oleate, diphenylmercury, zinc 2-ethylhexanoate, zinc naphthenate, nickelocene, hexacarbonylmolybdenum, cerium nitrate, vanadium trichloride, copper 2-ethylhexanoate, copper acetate, 2-ethyl Manganese hexanoate,
Metal catalysts such as zirconium 2-ethylhexanoate, zirconium naphthenate, triphenylarsenic, arsenic trichloride, boron trifluoride-diethyl ether complex, pyridine borane, calcium acetate, and barium acetate can be given.

Examples of the catalyst for the reaction between the hydroxyl group and the amino resin include acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid and dinonylnaphthalenedisulfonic acid, and amino neutralization of these acids. Products; adducts of these acids with epoxy compounds;

Polymer Composition According to the Present Invention The polymer composition of the present invention can be prepared by appropriately adding an organic solvent to the above-mentioned hydroxyl-containing siloxane polymer (A) and mixing.

The coating composition of the present invention may further contain, if necessary, for example, a coloring pigment, an extender pigment, a rust-preventive pigment, a dye,
Surfactants and other additives known per se, which are commonly used in paints, can also be added.

The polymer composition of the present invention thus obtained is excellent in lubricity by, for example, injecting it into an appropriate mold or applying it to an appropriate substrate surface to form a film, followed by crosslinking and curing. (Herein, the molded article also includes a molded article in the form of a film coated on a substrate).

The polymer composition of the present invention may be used as a coating composition, especially as a glass (eg, a vehicle windshield, a window glass, a window glass, a kagami, etc.), a metal (eg, an automobile, a vehicle, an aluminum fin, a passage). Sign board,
Microwave antennas, large water pipes, traffic lights, etc., plastics (films or sheets for greenhouse horticulture, artificial organs, toilet bowls, washbasins, etc.), inorganic materials (toilet bowls, bathtubs, tiles, etc.), base materials such as wood Useful for applying to surfaces.

The application of the polymer composition of the present invention to these substrates is carried out by a method known per se such as, for example, spray coating, brush coating, roller coating, roll coating, dip coating, curtain flow coater coating and the like. Can be. Further, the thickness of the applied film can be changed according to the use of the object to be coated, etc., but generally, the cured film thickness is preferably 1 to 100 μm, particularly preferably about 2 to 50 μm. .

The conditions for crosslinking and curing of the polymer composition of the present invention are determined according to the type of the hydrolyzable alkoxysilyl group-containing siloxane polymer (A) used in the preparation of the composition. Conditions at room temperature to about 300 ° C., preferably 50 to 200 ° C. for about 0.5 to about 40 minutes can be used.

The surface of the coating film formed by using the polymer composition of the present invention is excellent in lubricity. For example, the surface of an object coated with a conventional fluorinated ethylene-based resin may Is about 108 degrees and 20 μ
When the film on which the water droplet of L is attached is tilted at 70 degrees, the film falls due to its own weight.
Even when the water droplet is tilted to 0 degrees, the water droplet remains stopped and does not fall under its own weight, but the film formed from the polymer composition of the present invention has a contact angle of the water droplet of about 100 degrees and adheres to the film. A 20 μL water droplet started to slide under its own weight and dropped by only tilting the film at an angle within 20 degrees from the horizontal surface, and a 10 μL water droplet attached to the film inclined the film at an angle within 40 degrees from the horizontal surface. It shows an excellent water-sliding property in that it starts sliding under its own weight and falls.

Further, even after the film formed from the polymer composition of the present invention was immersed in water for 3 days, 20 μL of water droplets adhered to the film caused the film to move from the horizontal plane by 4 μL.
Just tilting at an angle within 0 degree starts to slide and drop by its own weight, and a 10 μL water droplet attached to the film starts to slide and drop by its own weight only by tilting the film at an angle within 50 degrees from a horizontal plane. It shows excellent durability of water slide.

Furthermore, even after being exposed outdoors for one month, the film formed from the polymer composition of the present invention can prevent water droplets of 20 μL from adhering to the film at an angle within 40 degrees from the horizontal plane. Just by tilting, it begins to slide under its own weight and falls, and 10 μL of water droplets attached to the film are:
It shows excellent water slide sustainability, in which the film starts sliding under its own weight and falls only by tilting the film at an angle within 50 degrees from the horizontal plane.

Thus, the polymer composition of the present invention is extremely useful as an object for which water droplets are not easily adhered or a surface treating agent for the object.

[0047]

According to the present invention, there is provided a polymer composition capable of imparting water repellency to the surface of an object, and at the same time, easily removing attached water droplets from the surface of the object.

[0048]

The present invention will be described more specifically with reference to the following examples. Hereinafter, simply “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Production Example 1 A four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping device was charged with 81.8 parts of n-butyl acetate, and heated at 95 ° C. under stirring. Next, a mixture consisting of 4.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), which is a monomer described in Table 1 and a polymerization initiator, was added dropwise at a temperature of 95 ° C. over 3 hours. . After dropping, 95 ° C
For 2 hours, solid content concentration 55%, number average molecular weight 7,
000 hydrolyzable alkoxysilyl group-containing siloxane polymer (A-1).

Production Examples 2 to 10 Except for using the monomer compositions shown in Table 1 below, siloxane polymers (A-2) to (A-1) were produced in the same manner as in Production Example 1.
0) was obtained. The special values of the obtained polymer are also shown in Table 1. Production Examples 7 to 10 are comparative production examples.

In Table 1, (Note 1) "Silaprene FM-0721": a methacryl group-containing siloxane macromonomer manufactured by Chisso Corporation, trade name, molecular weight of about 5,000, structural formula

[0052]

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(Note 2) “Silaprene FM-772”
1 ": a methacryl group-containing siloxane macromonomer, manufactured by Chisso Corporation, trade name, molecular weight about 5,000, structural formula

[0054]

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(Note 3) “Silaprene FM-072”
5 ": Chisso Corporation, methacryl group-containing siloxane macromonomer, trade name, molecular weight about 10,000, structural formula

[0056]

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(Note 4) “FAMAC”: a fluorine-containing monomer manufactured by Nippon Mektron, Ltd.

[0058]

[Table 1]

Examples 1 to 6 and Comparative Examples 1 to 4 Polymer compositions were obtained according to the formulations (solid contents) shown in Table 2 below.

In Table 2, (Note 5) “TPA90EX”: trade name, hexamethylene diisocyanate isocyanurate polymer, manufactured by Asahi Kasei Corporation, solid content 90%.

(Note 6) “U-100”: Nitto Kasei Corporation
"Neostan U-100", trade name, dibutyltin dilaurate.

The polymer compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were applied to a glass plate using a 30 μm applicator and heated under the conditions for forming a crosslinked coating film shown in Table 2. The test cured film was obtained by leaving it at room temperature for 3 days.

A performance test was performed on the obtained cured test film. Table 2 also shows the results. The test method in Table 2 is as follows.

State of coating film : The surface of the coating film was visually observed and evaluated according to the following criteria.

：: No abnormality was observed at all, ×: White turbidity was observed in the coating film.

Initial water contact angle : Using a CA-X type contact angle meter manufactured by Kyowa Interface Science Co., Ltd., about 10 mg of deionized water was used with a micro syringe at 23 ° C. and 65% RH. The solution was dropped on the film, and the angle between the film and the tangent to the edge of the water droplet was measured within 1 minute from the drop of the droplet.

Water contact angle 3 days after submersion : 4 cured films for test
After immersion in hot water of 0 ° C for 3 days, Kyowa Interface Science Co., Ltd.
23 ° C, 65% RH using CA-X type contact angle meter
Approximately 10 mg of deionized water was dropped on the film using a microsyringe under the atmosphere described above, and the angle between the film and the tangent to the end of the water droplet was measured within 1 minute from the dropping of the droplet.

Initial water sliding angle : Using a CA-X type contact angle meter manufactured by Kyowa Interface Science Co., Ltd., about 10 μL or about 20 μL of deionized water was added to a microsyringe in an atmosphere of 23 ° C. and 65% RH. Then, the glass plate was slowly tilted, and the angle at which water droplets started to slide was defined as the sliding angle.

3 days after water immersion : Water sliding angle : 4 cured films for test
After immersion in hot water of 0 ° C for 3 days, Kyowa Interface Science Co., Ltd.
23 ° C, 65% RH using CA-X type contact angle meter
Under the atmosphere of above, about 10 μL or about 20 μL of deionized water was dropped on the film using a microsyringe, and the glass plate was slowly tilted, and the angle at which the water droplets started to slide was defined as the sliding angle.

Water sliding angle one month after outdoor exposure : After the cured test film was exposed outdoors at Hiratsuka-shi, Kanagawa at 30 ° on the south side for one month, a CA-X contact made by Kyowa Interface Science Co., Ltd. was used. Using a goniometer, about 10μ in an atmosphere of 23 ° C and 65% RH.
L or about 20 μL of deionized water was dropped on the film using a microsyringe, and the glass plate was slowly tilted, and the angle at which the water droplet started sliding was defined as the sliding angle.

[0071]

[Table 2]

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4H020 BA32 4J027 AB10 AB18 AC03 AC04 AC06 AE04 AF05 AJ02 AJ08 BA02 BA03 BA04 BA05 BA06 BA07 BA08 BA10 BA12 BA13 BA14 BA15 BA17 BA18 BA19 BA20 BA21 BA22 BA23 BA24 BA26 BA27 CA10 CA25 CB00 CB08 CC02 CD08 4J038 CL001 DL121 KA03 KA04 NA07

Claims (10)

[Claims] (A) Formula (1) In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ²
Represents a divalent hydrocarbon group having 1 to 6 carbon atoms, R ³ represents a hydrogen atom or a methyl group, m represents a number of 6 to 300, and / or a compound represented by the formula: In the formula, R ⁴ and R ⁷ are the same or different and represent a hydrogen atom or a methyl group, and R ⁵ and R ⁶ are the same or different and have 1 carbon atom.
Represents a divalent hydrocarbon group of from 6 to 6, and n is a number of from 6 to 300.
% By weight, (b) 5 to 50% by weight of a hydrolyzable alkoxysilyl group-containing monomer, and (c) 10 to 94% by weight of another unsaturated monomer copolymerizable therewith. A polymer composition capable of forming a water-slidable surface, comprising a silyl group-containing siloxane polymer (A) as an essential component. 2. The method according to claim 1, further comprising a crosslinking agent (B).
A composition as described. 3. The composition according to claim 1, further comprising a curing catalyst (C). 4. A member having a water-slidable surface, on which a coating film of the composition according to claim 1 is formed. 5. The coating film surface has a property that when 20 μL of water is dropped, if the coating film surface is inclined within 20 degrees from a horizontal plane, water slides down.
A member having a water-slidable surface as described in the above. 6. The coating film surface according to claim 4, wherein, when 10 μL of water is dropped, if the coating film surface is inclined within 40 degrees from a horizontal plane, the water slides down.
A member having a water-slidable surface as described in the above. 7. The coating film surface has such a property that, even after being immersed in water for 3 days, when the coating film surface is inclined within 40 degrees from a horizontal plane when 20 μL of water is dropped, the water slides down. The member having a water-slidable surface according to claim 4, characterized in that: 8. The coating film surface has such a property that even when immersed in water for 3 days, when 10 μL of water is dropped, if the coating film surface is inclined within 50 degrees from a horizontal plane, the water slides down. The member having a water-slidable surface according to claim 4, characterized in that: 9. The coating film surface has a property that, even after being exposed outdoors for one month, when 20 μL of water is dropped, if the coating film surface is inclined within 40 degrees from a horizontal plane, water slides down. The member having a water-slidable surface according to claim 4, characterized in that: 10. The coating film surface has such a property that even after being exposed outdoors for one month, when 10 μL of water is dropped, if the coating film surface is inclined within 50 degrees from a horizontal plane, water slides down. The member having a water-slidable surface according to claim 4, characterized in that: