JPH11343321A - Polymer composition capable of forming water-slipping surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer composition capable of imparting a water- repellency by which adherent water drops can slip by mixing a cyclic-ether- group-containing siloxane polymer obtained by copolymerizing a siloxane macromonomer with a cyclic-ether-group-containing polymerizable monomer and other unsaturated monomers and a curing catalyst. SOLUTION: A siloxane macromonomer represented by formula I or II in an amount of 1-40 wt.% is copolymerized with 10-99 wt.% cyclic-ether-group- containing polymerizable monomer such as glycidyl (meth)acrylate and 0-89 wt.% other unsaturated monomers such as 2-hydroxyethyl (meth)acrylate to obtain a cyclic-ether-group-containing siloxane polymer having a number-average molecular weight of 1,000-100,000. The composition of this invention comprises 100 pts.wt. obtained siloxane polymer and 0.05-10 wt.% cationic polymerization catalyst such as triphenylsulfonium boron tetrafluoride. In the formulae, R<1> is a 1-10C alkyl; R<2> , R<5> , and R<6> are each a 1-6C divalent hydrocarbon group; R<3> , R<4> , and R<7> are each hydrogen or methyl; and (n) is the degree of polymerization and is 4-430.

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 by crosslinking and curing a specific cyclic ether group-containing siloxane polymer using a curing catalyst meets the above-mentioned object, and completed the present invention. Was.

Thus, according to the present invention, (A) (a)
formula

[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, and n Is 4 ~
430 and / or the formula

[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 4
1 to 40% by weight of a siloxane macromonomer represented by the following formula: (b) a polymerizable monomer having a cyclic ether group and, if necessary, (c) another unsaturated monomer copolymerizable therewith. A polymer composition capable of forming a water-slidable surface, comprising: a cyclic ether group-containing siloxane polymer obtained by polymerization; and (B) a curing catalyst.

[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 cyclic ether group-containing siloxane polymer (A) imparts water repellency to the surface of the crosslinked coating film, The following formula

[0015]

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(Where 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, Further, n means the average degree of polymerization of the dimethylsiloxane unit and is a number within the range of 4 to 430, preferably 6 to 100.) and / or the following formula:

[0017]

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Wherein 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; Further, n means the average degree of polymerization of the dimethylsiloxane unit, and is a number within the range of 4 to 430, 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.

Polymerizable monomer having cyclic ether group
(B) In the present invention, the polymerizable monomer (b) having a cyclic ether group used in the production of the cyclic ether group-containing siloxane polymer (A) provides a role as a crosslinking functional group with a crosslinking agent and water-slidability. It also has a role, and specific examples include an epoxy group and an oxetane group.

As the epoxy group-containing polymerizable monomer,
For example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (1,2-epoxy-4,7-methanoperhydroindene-5) (6) -yl) oxyethyl (meth) acrylate, 5,6-epoxy-4,7-methanoperhydroinden-2-yl- (meth) acrylate, 1,2-epoxy-4,7-methanoperhydroindene -5-yl- (meth) acrylate, 2,3-epoxycyclopentenyl (meth) acrylate, 3,4
-Epoxycyclohexylmethylated polycaprolactone (meth) acrylate, acrylic acid or methacrylic acid and dicyclopentadienedioxide, bis (2,3-
Epoxycyclopentyl) ether, epoxycyclohexene carboxylic acid ethylene glycol diester, bis (3,4-epoxycyclohexylmethyl) adipate, bis (4,5-epoxy-2-methylcyclohexylmethyl) adipate, ethylene glycol-bis (3,4- Epoxycyclohexanecarboxylate), 3 ', 4'-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-6-methylcyclohexylmethyl-
3,4-epoxy-6-methylcyclohexanecarboxylate, 1,2,5,6-diepoxy-4,7-methanoperhydroindene, 1,2-ethylenedioxy-bis (3,4-epoxycyclohexylmethane) And the like.

Examples of the oxetane group-containing polymerizable monomer include, for example,

[0023]

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(Wherein R ⁸ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorine atom, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, an aralkyl group, a furyl group, or a phenyl group) The complementary functional group which reacts complementarily with the hydroxyl group in the above formula, but does not substantially react with the oxetane group, for example, an isocyanate group;
It has a lower alkoxy group (for example, methoxy, ethoxy), a lower alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl) and the like together and a radically polymerizable unsaturated group, for example, an acroyl group, a methacryloyl group, and a vinyl group at the other end. Can be obtained by reacting the compound with an unsaturated compound.

Compounds of the above formula, for example 3-ethyl-3-
Hydroxymethyloxetane can be produced by reacting trimethylolpropane with diethyl carbonate to produce a hydroxyl group-containing cyclic carbonate, followed by decarboxylation.

The unsaturated compound to be reacted with the compound of the above formula includes, for example, (meth) acrylic acid,
Examples thereof include methyl (meth) acrylate, ethyl isocyanate (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, methyl vinyl ether, and ethyl vinyl ether.

Other unsaturated monomers (c) Other unsaturated monomers (c) which can be copolymerized with the siloxane macromonomer (a) and the polymerizable monomer having a cyclic ether group (b) if necessary include a crosslinking reaction. Can be used without any particular limitation as long as it does not hinder the reaction. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxyalkyl (meth) acrylate and hydroxybutyl (meth) acrylates such as hydroxyalkyl (meth) acrylates having 2 to 8 carbon atoms; polyether polyols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; and (meth) Monoesters with unsaturated carboxylic acids such as acrylic acid; hydroxyalkyl vinyl ethers;
Adducts of allyl alcohol, hydroxyalkyl esters of (meth) acrylic acid, (poly) alkylene glycol mono (meth) acrylate, and lactones (eg, ε-caprolactone, γ-valerolactone, δ-valerolactone); polyethylene Monoether of a polyether polyol such as glycol, polypropylene glycol or polybutylene glycol with a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth) acrylate; α, β-unsaturated carboxylic acid;
Adducts with monoepoxy compounds such as (Shell Chemical Co., Ltd.) and α-olefin epoxides; glycidyl (meth)
Adducts of acrylates with monobasic acids such as acetic acid, propionic acid, pt-butylbenzoic acid, fatty acids; unsaturated compounds containing an acid anhydride group such as maleic anhydride or itaconic anhydride; Monoester or diester with glycols such as 1,6-hexanediol and neopentyl glycol; hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether; hydroxyl-containing unsaturated monomers such as allyl alcohol; acrylic acid, methacrylic acid Carboxyl group-containing unsaturated monomers such as, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate; ) Methyl Le acid, (meth) acrylate, (meth) acrylic acid n- propyl, isopropyl (meth) acrylate, (meth) acrylic acid n- butyl,
Isobutyl (meth) acrylate, t (meth) acrylate
-Butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Meta)
C1-C18 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as cyclohexyl acrylate; methoxybutyl (meth) acrylate,
C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxyethyl (meth) acrylate and ethoxybutyl (meth) acrylate; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, t-butyl Chain alkyl vinyl ethers such as 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; benzyl vinyl ether and phenethyl vinyl ether Aralkyl vinyl ethers: allyl glycidyl ether, allyl ethyl ether Allyl ethers such as ter; vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate, and veova monomer (manufactured by Shell Chemical Company) Vinyl esters; propenyl esters such as isopropenyl acetate and isopropenyl propionate; ethylene, propylene, butylene,
Olefinic compounds such as vinyl chloride; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- Hydrolyzable alkoxysilyl group-containing monomers such as (meth) acryloyloxypropyltrimethoxysilane, vinyltriacetooxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, and γ- (meth) acryloyloxypropyltriethoxysilane; Allyl monomers such as diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, diallyl tetrabromophthalate, pentaerythritol diallyl ether, and allyl glycidyl ether;
Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) 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, Data pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate 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,
Examples thereof include (meth) acrylates of polyhydric alcohols such as pentaerythritol diallyl ether and divinylbenzene.

Cyclic ether group-containing siloxane polymer
(A) In the present invention, the cyclic ether group-containing siloxane polymer (A) includes the siloxane macromonomer (a) described above,
It can be obtained by copolymerization of the cyclic ether group-containing polymerizable monomer (b) and, if necessary, another unsaturated monomer (c) copolymerizable therewith.

The copolymerization ratio of the siloxane macromonomer, the cyclic ether group-containing polymerizable monomer, and other unsaturated monomers copolymerizable therewith, if necessary, depends on the physical properties desired for the obtained cyclic ether group-containing siloxane polymer (A). Can be varied over a wide range depending on the total amount of the above-mentioned monomers.

Siloxane macromonomer (a): 1-4
0% by weight, in particular 3 to 25% by weight, cyclic ether group-containing polymerizable monomer (b): 10 to 99% by weight, especially 12 to 70%
% By weight Other unsaturated monomer (c): 0 to 89% by weight, particularly 5 to
The copolymerization of the above monomers is usually carried out in an organic solvent in the presence of about 0.01 to about 10 parts by weight of a polymerization initiator per 100 parts by weight of the total amount of the monomers, from about -20 ° C to about -20 ° C. 160 ° C
At normal pressure or in some cases about 30 kg / cm ² G
The reaction can be carried out under pressure up to.

The cyclic ether group-containing siloxane polymer (A) thus obtained is generally 1,000 to 100,
000, preferably in the range of 3,000 to 50,000.

Curing Catalyst (B) In the present invention, as a curing catalyst (B) for cross-linking and curing the cyclic ether group-containing siloxane polymer (A), a cationic polymerizable catalyst or a hydrolyzate directly bonded to a silanol or silicon atom is used. A composite catalyst of a silicon compound having a decomposable group and an aluminum chelate compound is used.

The above-mentioned cationic polymerizable catalyst is appropriately selected in order to obtain a composition in which the required crosslinking temperature and the storage stability of the target composition are balanced. For example, a quaternary ammonium salt type catalyst can be used. A compound N, N-dimethyl-N-benzylanilinium antimony hexafluoride,
N, N-dimethyl-N-benzylanilinium boron tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride ,
N, N-dimethyl-N- (4-methoxybenzyl) toluidinium antimony hexafluoride and the like; triphenylsulfonium boron tetrafluoride which is a sulfonium salt type compound,
Examples include triphenylsulfonium antimony hexafluoride; phosphonium salt type compounds such as ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride; and iodonium salt type compounds such as diphenyliodonium arsenic hexafluoride. it can. The blending amount of the cationic polymerization catalyst is not particularly limited, but generally, 0.05 to 10 parts by weight is suitable per 100 parts by weight of the cyclic ether group-containing siloxane polymer (A).

Among the composite catalysts of a silanol or a silicon compound having a hydrolyzable group directly bonded to a silicon atom and an aluminum chelate compound, examples of the silicon compound having a hydrolyzable group directly bonded to silanol or a silicon atom include: A compound having a silanol group such as diphenylsilanediol or a compound having a hydrolyzable group which hydrolyzes in the presence of water to form a silanol group which is a hydroxy group directly bonded to a silicon atom, for example, Si (OR) ₄ (R is the same or different and represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms); a silicon monomer; a low-condensation product of a silicon monomer, for example, “Colcoat ES40” (manufactured by Colcoat Co., Ltd.) Pentamer of tetraethyl silicate). The amount of the silanol or the silicon compound having a hydrolyzable group directly bonded to a silicon atom is not particularly limited, but generally, the cyclic ether group-containing siloxane polymer (A) 1
0.1 to 50 parts by weight per 100 parts by weight is suitable.

Examples of the aluminum chelate compound include tris (ethylacetoacetate) aluminum, tris (isopropylacetoacetate) aluminum, and isopropoxybis (ethylacetoacetate) aluminum. The aluminum chelate compound is used in an amount of 0.01 to 100 parts by weight based on a total of 100 parts by weight of the cyclic ether group-containing siloxane polymer (A) and silanol or a silicon compound having a hydrolyzable group directly bonded to a silicon atom.
30 parts by weight are suitable.

Polymer Composition According to the Present Invention The polymer composition of the present invention comprises the cyclic ether group-containing siloxane polymer (A) and the curing catalyst (B) described above.
Can be adjusted by appropriately adding and mixing an organic solvent.

The polymer composition of the present invention may further contain, if necessary, additives known per se, such as coloring pigments, extender pigments and rust-preventive pigments, which are known per se. At that time, the addition of a substance that inhibits the crosslinking reaction of the polymer composition of the present invention must be avoided. Examples of the substance that inhibits the crosslinking reaction of the polymer composition of the present invention include basic substances. When a pigment or the like is added, it is necessary to consider a surface treatment agent or the like of the pigment.

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, in particular, as a coating composition for glass (eg, vehicle windshield, window glass, window glass, kagami, etc.), metal (eg, automobile, vehicle, aluminum fin, 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 10 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 hydroxyl-containing siloxane polymer (A) and the crosslinking agent component (B) used in the preparation of the composition. In general, conditions of from normal temperature to about 300 ° C., preferably 80 to 250 ° C. for about 0.5 to about 40 minutes can be used.

The surface of the molded article formed by using the polymer composition of the present invention is excellent in slipperiness,
For example, the surface of an object coated with a conventional fluorinated ethylene resin has a contact angle of water droplets of about 108 °, but water droplets stopped even when the film with a mass of 10 mg of water droplets was inclined at 90 °. The film formed from the polymer composition of the present invention has a contact angle of water droplets of about 100 °, and a water droplet having a mass of 10 mg attached to the film causes the film to move from the horizontal plane. It shows excellent water-slip properties such that it starts to slide under its own weight and falls when it is only tilted at an angle within 40 °. Further, even after the film formed from the polymer composition of the present invention was immersed in water for 3 days, water droplets having a mass of 10 mg attached to the film only tilted the film at an angle within 50 ° from the horizontal plane. In this way, it shows excellent water slide sustainability, starting to slide under its own weight and falling.

As described above, the polymer composition of the present invention is extremely useful as an object for preventing adhesion of water droplets or a surface treating agent for the object.

[0044]

According to the present invention, there is provided a coating material capable of imparting water repellency to the surface of an object and at the same time allowing water droplets attached to the object surface to be easily slid off from the surface of the object.

[0045]

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 53.8 parts of xylene and 28 parts of methyl isobutyl ketone, heated under stirring, and maintained at 115 ° C. Was. Next, at 115 ° C., a mixture composed of the monomers shown in Table 1 and 4.2 parts of azobisisobutyronitrile as a polymerization initiator was added dropwise over 3 hours. After dropping, 1
After aging at 15 ° C for 2 hours, a solution of an epoxy group-containing siloxane polymer (A-1) having a solid content of 55% and a number average molecular weight of 14,000 was obtained.

Production Examples 2 to 7 A siloxane polymer having a cyclic ether group (A) was prepared in the same manner as in Production Example 1 except that the monomer compositions shown in Table 1 below were used.
-2) to (A-5) and Comparative Polymer (A-6)
A solution of (A-7) was obtained. The special values of the obtained polymer are also shown in Table 1.

In Table 1, (Note 1) "Silaprene FM-7711": a methacryl group-containing siloxane macromonomer manufactured by Chisso Corporation, trade name, molecular weight of about 1,000, structural formula

[0049]

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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

[0051]

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(Note 3) “Silaprene FM-772”
5 ": Chisso Corporation, methacryl group-containing siloxane macromonomer, trade name, molecular weight about 10,000, structural formula

[0053]

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(Note 4) “Silaprene FM-072”
1 ": a methacryl group-containing siloxane macromonomer, manufactured by Chisso Corporation, trade name, molecular weight about 5,000, structural formula

[0055]

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[0056]

[Table 1]

Examples 1 to 12 and Comparative Examples 1 to 4 The cyclic ether group-containing siloxane polymer (A) and the curing catalyst (B) were mixed and stirred according to the blending (solid content) shown in Table 2 below to obtain a polymer composition. I got

In Table 2, (Note 5) "SI-100": trade name, manufactured by Sanshin Chemical Co., Ltd., antimony-based cationic polymerization catalyst.

(Note 6) “CI-2946”: trade name, manufactured by Nippon Soda Co., Ltd., an antimony-based cationic polymerization catalyst.

(Note 7) “Aluminum chelate A”: trade name, manufactured by Kawaken Fine Chemical Co., Ltd., aluminum trisacetylacetonate.

(Note 8) “SX-11”: trade name, diphenylsilanediol, manufactured by Shin-Etsu Chemical Co., Ltd.

The polymer compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 4 were coated on a glass plate using a No. 10 bar coater, and heated under the conditions for forming a crosslinked coating film shown in Table 2. Thus, a cured film was obtained. The two-cone hardness of the cured film, and the contact angle and the sliding angle of the film immediately after preparation and the film after immersion in water for 3 days were measured by the following methods. Table 2 also shows the results.

Two-cone hardness: 4 places the coated plate in a constant temperature room at 20 ° C.
After standing for a time, the measurement was carried out using a TUKON microhardness tester manufactured by American Chain & Cable Company. The hardness increases as the numerical value increases.

Contact angle : CA- manufactured by Kyowa Interface Science Co., Ltd.
Using an X-type contact angle meter, about 10 mg of deionized water was dropped on the film using a microsyringe under an atmosphere of 23 ° C. and 65% RH, and the angle formed by the film and the tangent to the end of the water droplet. Was measured within one minute from the dropping of the droplet.

Slope angle : CA- manufactured by Kyowa Interface Science Co., Ltd.
Using an X-type contact angle meter, under an atmosphere of 23 ° C. and 65% RH, about 10 mg of deionized water is dropped on the film using a micro syringe, and the glass plate is slowly tilted, and the water droplets slide. The starting angle was defined as the sliding angle.

[0066]

[Table 2]

[0067]

[Table 3]

Claims (10)

[Claims] (1) Formula (A) (a) 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, n represents a number of 4 to 430, 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 4 to 430.
% By weight, (b) a polymerizable monomer having a cyclic ether group, and if necessary, (c) a cyclic ether group-containing siloxane polymer obtained by copolymerization with another unsaturated monomer copolymerizable therewith, and (B) curing A polymer composition capable of forming a water-slidable surface, comprising a catalyst. 2. The polymer composition according to claim 1, wherein the cyclic ether group of the monomer (b) is an epoxy group. 3. The polymer composition according to claim 1, wherein the cyclic ether group of the monomer (b) is an oxetane group. 4. The polymer composition according to claim 1, wherein the curing catalyst (B) is a cationic polymerization catalyst. 5. The polymer composition according to claim 1, wherein the curing catalyst (B) is a composite catalyst of a silicon compound having a silanol group or a hydrolyzable group directly bonded to a silicon atom and an aluminum chelate compound. 6. The polymer composition according to claim 1, wherein a water droplet having a mass of 10 mg on the surface can form a film that starts sliding at an inclination angle of 40 ° or less from a horizontal plane by its own weight. 7. The film according to claim 1, wherein even after being immersed in water for 3 days, a water droplet having a mass of 10 mg on its surface can form a film which starts sliding at an inclination angle of 50 ° or less from a horizontal plane by its own weight. Polymer composition. 8. A coating composition comprising the polymer composition according to claim 1. 9. A molded article having a water-slidable surface formed from the polymer composition according to claim 1. 10. The molded article according to claim 1, which is in the form of a film.