WO2003093388A1

WO2003093388A1 - Surface treating composition excellent in water repellency and water sliding property

Info

Publication number: WO2003093388A1
Application number: PCT/JP2003/005316
Authority: WO
Inventors: Yonb-Bo Chong; Shinichirou Kobayashi; Yasuo Itami
Original assignee: Daikin Industries, Ltd.
Priority date: 2002-04-30
Filing date: 2003-04-25
Publication date: 2003-11-13
Also published as: AU2003231512A1; JP4175323B2; JPWO2003093388A1

Abstract

A surface treating composition which comprises a binder resin having water repellency, polytetrafluoroethylene particles and a dispersant, and optionally particles having a low heat capacity and a solvent. The surface treating composition provides a coating film which exhibits extremely small sliding fall angle for a fine water droplet, is easy to slide water droplets and exhibits high water repellency, and thus can prevent icing and adhesion of snow.

Description

Akira Itoda Composition for surface treatment that excels in water repellency and water slippage

The present invention relates to a composition for surface treatment capable of imparting surface characteristics excellent in water repellency and slipperiness. Background art

Various appliances, equipment, buildings and parts installed outdoors will cause icing or snowfall during the winter, which may degrade the original function, cause damage or even cause injury. Sometimes. In order to prevent such icing and snowing, various surface treatments are conventionally performed.

For example, a method of forming fine irregularities on the surface, a method of applying an anti-icing agent to the surface, and a method of providing an anti-icing layer on the surface are known.

Of these, the method of providing an icing (anti-snow) layer on the surface is mainly studied in the direction of preventing icing (snow) by increasing the water repellency of the surface (increasing the water contact angle). ing. For example, Japanese Patent Application Laid-Open No. 8-3477 discloses a water-repellent water-containing resin in which terminal fluorinated polytetrafluorinated ethylene (PTFE) powder having a molecular weight of 500 to 2500 is mixed in a non-fluorinated resin. It is described that paint is used to prevent snowfall. Further, in JP-A-8-349, terminally fluorinated PTFE powder having a molecular weight of 500 to 200,000 is contained in a liquid resin (for example, fluororesin, silicone resin, polyester resin). It is described that snow is prevented using compounded anti-snow coating. However, it is difficult to uniformly disperse the PTFE powder in the resin, and a portion with low water repellency remains on the surface, which may impair the snow prevention effect.

As a result of investigations by the present inventors, it has been found that simply increasing the water repellency of the surface is insufficient to effectively prevent icing or snowing. As a result of further research and observation of the phenomena that occur, when the water repellency is high, the water droplets formed on the surface certainly become close to spherical and the large water droplets slide down, for example, 4 liters or less It was found that the water droplets did not slide down and freeze on the surface, which became the core and the icing progressed. The same phenomenon is considered to have occurred for snowfall.

Therefore, the inventors examined how much the sliding angle should be for sliding down the micro water droplet which may become the core of icing, and further, a large amount of experiments on the surface treatment composition giving such a low sliding angle surface As a result of the study, the present invention has been completed. Disclosure of the invention

That is, the present invention

(A) Water-repellent binder resin,

(B) PTFE particles, and

(C) Dispersant

The present invention relates to a composition for surface treatment which provides a coating film having an initial sliding angle of 15 degrees or less at the sliding angle defined below.

Record

(1) 4 ^ liters of distilled water is dropped on a sample plate placed horizontally in an environment with a temperature of 17 ± 1 ° C and a relative humidity of 60 ± 2% to form a water droplet, and then the sample plate is The angle of the sample plate when the water droplet starts rolling Let the degree be the sliding angle.

In the present invention, (D) particles of low heat capacity may be further included, and (E) a solvent may be included.

As the water-repellent binder resin (A), a fluorine resin is preferred, and in particular

(1) Formula (I):

-CF ₂ -CFX- (I)

(In the formula, X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group) Fluorofluorinated structural unit (1),

(2) Formula (II):

_CH ₂ -CR (CH ₃ )-(II)

(Wherein R is an alkyl group having 1 to 8 carbon atoms)] 3-Methyl-substituted α-modified structural unit (2),

(3) Structural units based on monomers having a chemically curable reactive group (3)

(4) Structural units based on monomers having an ester group in the side chain (4), and

(5) Structural units based on other copolymerizable monomers (5)

Consisting of 20 to 60 mol% of the structural unit (1), 5 to 25 mol% of the structural unit (2), 1 to 45 mol% of the structural unit (3) and 1 to 45 mol of the structural unit (4) % And a fluorine-containing fluorine-containing compound having a number average molecular weight of 1000 to 500,000 in which the structural unit (5) is contained in an amount of 0 to 45 mol% (provided that the total of structural units (1) + (2) is 40 to 90 mol%) Copolymers are preferred.

Further, as the PTFE particles (好ましく), those having an average particle diameter in the range of 1 m to 10 m are preferable, and the weight average molecular weight is in the range of 500 to 500,000, and further preferably 500 to 20,000. Some are preferred.

As the dispersant (C), vinyl monomers having a perfluoroalkyl group Polymers containing recurring units derived from one molecule are preferred, and copolymers of the recurring units with non-fluorinated vinyl monomers are particularly preferred.

As the particles (D) having a low heat capacity which is an optional component, particles having a molar heat capacity of 30 C a ZJK- ¹ mo ¹ or less are preferable, and the average particle diameter is in the range of 2 im or more and 12 m or less. The ones in are preferred.

Such low heat capacity particles (D) include, for example, carbon black particles, and further, crystalline single carbon black particles.

The solvent (E) as an optional component is preferably an organic solvent-based solvent, more preferably a solvent system in which two or more organic solvents are present, particularly a solvent system containing a polar organic solvent and a nonpolar organic solvent.

The preferable compounding ratio in the surface treatment composition of the present invention is the water-repellent binder resin (A) 100 parts by weight (hereinafter the same unless otherwise noted), and the polytetrafluoroethylene particles (B). Is 50 parts by weight or more and 400 parts by weight or less, and the dispersant (C) is 5 parts by weight or more and 100 parts by weight or less. When blending particles (D) of low heat capacity, 25 parts by weight or more and 400 parts by weight or less, and when solvent (E) is used, 400 parts by weight or more and 4,00 parts by weight or more It is preferable to set it below.

The composition of the invention is preferably in the form of a paint.

The composition of the present invention may further contain a crosslinking agent (F). In that case, the water-repellent binder resin (A) is a resin having a chemical curing reactive group. The crosslinking agent (F 2) is preferably incorporated in an amount of 0.1 equivalent or more and 5 equivalents or less with respect to 1 equivalent of the chemical curing reactive group in the water-repellent binder resin having a chemical curing reactive group.

Furthermore, a preferred composition of the present invention provides a coating having an initial micro water droplet sliding angle of not more than 15 degrees, as defined below.

Record (2) 1 liter of distilled water is dropped on a sample plate placed horizontally in an environment with a temperature of 17 ± 1 ° C and a relative humidity of 60 ± 2% to form a water droplet, and then the sample plate is angled Tilt it one degree at a time, and let the angle of the sample plate when the water droplet begins to roll be the sliding angle of the ultra-small water droplet. BEST MODE FOR CARRYING OUT THE INVENTION

Each component which comprises the composition of this invention is demonstrated.

(A) Water-repellent binder resin

The water repellent binder resin is water repellent, and the sliding angle of the coating film surface obtained from the composition of the present invention (definition (1): 4 liter water droplet, first time, same hereafter) is 15 degrees or less, It may be any resin that preferably has a temperature of 10 degrees or less, more preferably 5 degrees or less. Therefore, the sliding angle of the coating surface of the resin (A) alone does not necessarily have to be 15 degrees or less.

Furthermore, the ultrafine water droplet sliding angle (definition (2): water droplet of 1 z liter. First time, the same shall apply hereinafter) is less than 15 degrees, preferably less than 12 degrees, more preferably less than 10 degrees. Especially preferred. The sliding angle of a 1-liter ultrafine water droplet can be evaluated more by the index of the sliding angle, compared with the measurement of the sliding angle of a 4-liter water droplet.

Further, as the degree of water repellency, it is desirable that the contact angle to water is large, and it is preferable that the contact angle to water of the coating film surface obtained from the composition of the present invention be 140 degrees or more. However, although it is not necessary for the contact angle to water of the single coating film surface of resin (A) to be 140 degrees or more, the surface having a target water repellency of 100 degrees or more is on the treated surface. It is preferable from the point which is easy to provide. The upper limit is theoretically 180 degrees. Examples of such a binder resin (A) include fluorine resin, silicone resin, urethane resin and the like, and fluorine resin is preferable from the viewpoint of excellent dispersibility of PTFE particles and the like. The fluorine resin can be selected from conventionally known fluorine resins, but is advantageous for weatherability, coating, solvent solubility and the like, so tetrafluoroethylene (TFE), black-mouthed trifluoroethylene Copolymers based on (CTFE) and hexafluoropropylene (HFP) are preferred. The following are suitable as these fluororesins (in some cases, they may overlap).

(1) A copolymer comprising fluorolefin, cyclohexyldiether, alkylbiether and hydroxyalkyl vinyl ether as essential components, which is fluorolefin, cyclohexyl vinyl ether The content of units based on alkyl vinyl ether, hydroxyalkyl vinyl ether and other comonomers is 40 to 60 mol%, 5 to 45 mol%, 5 to 45 mol%, 3 to 15 mol% and 0 to 40 mol%, respectively. A room-temperature curable fluorine-containing copolymer having an intrinsic viscosity of 0.1 to 2. 0 d 1 / g which is 30 mol% and which is measured at 30 ° C. in tetrahydrofuran in an uncured state -34107).

As a specific example, cro-ported trifluoroethylene (CTFE) / cyclohexyl vinyl ether (c-HVE) / ethyl vinyl ether (EVE) / hydroxypyl vinyl ether (HBVE) copolymer, tetrafluorinated ethylene (TFE) / c —HVEZEVEZHBVE copolymer, CTF EZc—HVEZ iso-peptizable vinyl ether (i-BVE) / HBVE copolymer and the like.

(2) Fluoroolephine, carboxylic acid beer ester, alkyl vinyl ether and hydroxyalkyl vinyl ether as essential monomers, and as an optional component, copolymerize other vinyl monomers copolymerizable with these monomers Vinyl copolymer (described in JP-A-62-7767). A specific example is: Hexafluoropropylene (HFP) / EVE / HB VE / VA 9 (trade name: Carboxylic acid vinyl ester manufactured by Shell Chemical Co., Ltd.) Copolymer, HFPZEVEZHBVE / Vinyl benzoate (VBz) copolymer, CTFE ZEVE / HBVE / Baber 9 copolymer, TFE / EVEZ HBVEZVB z copolymer, HFP / i-I B VE / HB VEZ pivalinate vinyl ( PIV) Copolymer, HFP / EVE / hydroxyhexyl vinyl ether (HHVE) Zp-vinyl t-butylbenzoate (VPTBz) co-weight

VCHC) copolymer, CTFE / EVE / HBVEZP IV copolymer and the like.

(3) Formula:

— CC 1 F — CF. One

35 to 65 mol% of the structural unit represented by the formula:

One CH. One CH_

I

01 c = o

I

R ¹ — C 1 R ³

I

R ²

(Wherein R ¹ R ² and R ³ are the same or different and are 5 to 50% by mole of the structural unit represented by the alkyl group having 1 to 10 carbon atoms)

CH ₂ - -

01 R ⁴ O H

(Wherein R ⁴ is an alkylene group having 2 to 5 carbon atoms) A fluorine-containing copolymer comprising 1 to 30 mol% of the structural unit (described in JP-A-62-174213).

As a specific example, CTFE Z Vaba 10 (trade name: Forced Rubbonic Acid Vinyl Ester manufactured by Shell Chemical Co., Ltd.) / HBVE copolymer, CTFE Z Vaba 10 / CH ₂ CHCH ₂ CH ₂ (CF ₂ ) ₂ H Copolymer, CTFE / Baber 10ZH BVE copolymer and the like can be mentioned.

(4) Fluorene and alkenes and formulas:

CH ₂ = CH-CH ₂ -0-R

(Wherein R is — (CH ₂ CXHO) _n — H, n is an integer of 0 to 6, X is H or CH ₃ ), and it is composed of a hydroxy group-containing aryl ether represented by fluoroolefin, algen and hydroxyl group-containing A fluorine-containing resin having a content of units based on faryl ether of 25 to 75 mol%, 10 to 70 mol% and 3 to 40 mol%, respectively (as described in JP-A 2-265979).

As specific examples, CTFE / propylene / ethylene glycol monoaryl ether (EGMAE) / vinyl acetate (VAA) copolymer, CTFEZ ethylene ZEGMAE / VAA copolymer, CTF EZ isobutylene ZEG MAEZVAA copolymer, CTFE Z propylene / EGMAE copolymer, CTF EZ propylene / aryl alcohol / VAA copolymer, TF EZ ethylene / EGMAE / VAA copolymer, etc. may be mentioned.

(5) 25 to 75% by mole of fluorefluorine, 10 to 70% by mole of fatty acid beer ester, 3 to 40% by mole of alkylene glycol monoallyl ether and 0 to 20% by mole of a vinyl group-containing vinyl monomer A copolymer having a hydroxyl value in the range of 60 to 20 Omg KOH / g (as described in JP-A-2-298645).

Specific examples include CTFE Z vinyl acetate (VAc) / EGMAE / VA A copolymer, CTFE / VA c / diethylenediaryl monoallyl ether / VAA copolymer, CTFE / VAc / E GM AE copolymer, etc. Be

(6) (6-1) Formula (I):

One CF ₂ — CFX_ (I) (In the formula, X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group) Fluoro olef structural unit (6-1),

(6-2) Formula (II):

_ CH ₂ -CR (CH ₃ )-(II)

(In the formula, R is an alkyl group having 1 to 8 carbon atoms); 8-methyl-substituted monovalent lefin structural unit (6-2),

(6-3) Structural units based on monomers having a chemically curable reactive group (6-3),

(6-4) Structural units based on monomers having an ester group in the side chain (6-4), and

(6-5) Structural units based on other copolymerizable monomers (6-5)

And the structural unit (6-1) is 20 to 60 mol%, the structural unit (6-2) is 5 to 25 mol%, the structural unit (6-3) is 1 to 4 mol%, the structure The unit (6-4) is 1 to 45 mol% and the structural unit (6-5) is 0 to 4 mol% (however, the total of the structural units (6-1) + (6-2) is 40 to A fluorine-containing copolymer having a number average molecular weight of 1000 to 500, which is 90 mol% (described in JP-A-4-25062).

As a typical example of the structural unit (6-3) based on a monomer having a chemically curable reactive group, a Biel unit amount in which the curable reactive group is a hydroxyl group, an epoxy group, an epoxy group, a silyl group, etc. Body and the like.

As a vinyl monomer having a curing reactive group of hydroxyl group, for example, hydroxyalkyl vinyl ether, hydroxyalkyl vinyl ester and the like can be mentioned.

Examples of the carboxyl group-containing vinyl monomer include crotonic acid, maleic acid, acrylic acid, methacrylic acid, itaconic acid, vinyl acetic acid, and monomers derived therefrom.

Examples of epoxy group-containing Biel monomers include, for example, JP-A-2-23225. Examples thereof include those described in JP-A-0, JP-A-2-232251, and the like. For example, an epoxy vial or epoxy vinyl ether represented by the following formula can be exemplified.

CH ₂ = CH-R ⁵ -R ⁶ H

(Wherein, R ⁵ is one CH ₂ -〇 one R ^7, - CH ₂ -〇- R ⁷ - C-,

OH

— ○ — R ⁷ — or one R ⁷ — (where R ⁷ is an alkylene group),

R ⁸

R ⁶ is one C—CH. (However, R ⁸ is a hydrogen atom or an alkyl group),

\ / ·

O))

Specific examples of these are, for example, the following monomers,

H ₂ ⁼ H H H H O H H H H H H H H H H H H H O H H H O H H H H H H H O H H H H H H H H O H

\ /

o

CH ₂ = CH-CH ₂ -CH-CH ₂

\ /

Yes

,

Examples of the silyl group-containing vinyl monomer include those described in JP-A-61-141713, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriproxysilane, vinylmethyl. Dimethoxysilane, Vinyldimethylmethoxysilane, Vinylmethyldiethoxysilane, Vini J Retris (amethoxy) silane, Trimethoxysilylphenylvinylether, Triethoxysilylethyvinylether, Trimethoxysilylbutylvinylether, Triethoxysilylbutynyl Vinyl Ether Methoxy silyl propyl Biel ether, tri-hydroxy silyl propyl Biel ether, vinyl tri isopropenyl oxysila , Vinylmethyldiisopropyyloxysilane, triisopropyoxysilylvinyl ether, triisopropenyloxysilylpropyl vinyl ether, triisopropyoxysilylbutyl vinyl ether, vinyltris (dimethyliminooxy) Silane, vinyl tris (methyl ethyl imino oxy) silane, pinyl methyl bis (methyl dimethyl amino) silane, vinyl dimethyl (dimethyl imino oxy) silane, tris (dimethyl imino oxy) silyl ether, methyl bis (dimethyl dimethyl Iminooxy) silyl ethyl vinyl ether, tris (dimethyl imino oxy) silyl propyl vinyl ether, 7- (meth) acryloxy provir trimethoxysilane, 7- (meth) acrylylo Hydroxypropyltriethoxysilane, r- (Meth) acryloyloxypropyl methyl dimethoxysilane, 7- (Meth) acryloyloxypropyl 卜 Liisopropyyloxysilane, 一 (Meth) acryloyloxypropyl Rutris (dimethyliminooxy) silane, 7- (meth) acryloyloxypropyltris (dimethyliminooxy) silane, aryltrimethoxysilane and the like can be mentioned.

As a specific example, CTFEZ isopuprylene (IB) ZHBVEZ pinic acid propionate (VP i) copolymer, CTFE / IB nohydroxy ethyl ether (HEAE) / V Ac copolymer, TFEZ IB / HB VE / VP i Copolymer, CTFE / I BZHBVEZ 9-copolymer, TFE / IB / HB VEZVB z copolymer, CTFE / I BZHBVEZ jetyl maleate (DEM) copolymer, TFE / I BZHBVE / Veaber 9-Dibutyl maleate (DBM) copolymer, CTFE ZI BZHBVE / jetyl fumarate (DEF) copolymer, CTFE ZI B / hydroxyl vinyl ether (HEVE) / dibutyl fumarate (DBF) copolymer, H FP / I BZHBVE / VB z copolymer, TFEZ 2-methyl-1 pen Ten (MP) / HBVE / VP i copolymers, TFE / IB / HBVE / VP i / CH 2 = CH (CF 2) P CF 3 (p = l~5) copolymers, TFE / IB / HBVE / VP i ZVB z copolymer, CTFE / IB / HBVE / VAc copolymer, TFEZI B / HBVE / t-butyl vinylbenzoate (V t B z) copolymer, TFE / IB / HBVE / VP i / DEM copolymer, CTFE / IB / HBVE / VB z / DEF copolymer, CTFE / I / HBVE / VP i / CH 2 = CH (CF 2) P CF 3 (p = l~5) copolymers, CTFE / MP / H EVE / VP i copolymer, TFE / IB / HBV E / VP i / bieracetic acid (VAA) copolymer, TFEZ B / HEVE / VAc ZVAA copolymer, TFE / IB / HBVE / VP i ZVB z / co-tononic acid (CA) copolymer, TFE / I BZHBVE / Bavar 9 / CA copolymer, TFE Z I BZHB VEZ baer 9 ZVB z / CA copolymer, T FEZ IB / HBVE / V 10 / V t B z / CA copolymer, TFE / IB / HBVE / V t B z / CA copolymer, TFE / IB / HBVE / D EM / CA copolymer, TFE / IB / HB VE / DFM / CA copolymer, TFE / MP / HBVE / VP i ZVAA copolymer and the like.

Examples of commercially available products containing the fluororesins of (1) to (6) include Zeffle (manufactured by Daikin Industries, Ltd.), Lumiflon (manufactured by Asahi Glass Co., Ltd.), and Fluorate (manufactured by Dainippon Ink and Chemicals, Inc.) Cefralco rice cake (manufactured by Central Glass Co., Ltd.) and the like.

Among the fluorine resins of (1) to (6), the fluorine-containing copolymer of (6) is preferable from the viewpoint of heat resistance.

Specific examples of resins other than the fluorine resin suitable for the water repellent binder resin include, for example, a silicone resin which may be fluorinated.

(B) PTFE particles

As the PTFE particles (B), the weight average molecular weight is 500 or more, 500, Those less than or equal to 000 are preferred. Usually, PTFE has a weight average molecular weight of 1,000,000 to 10,000,000. However, since PTFE in this range is fibrillated when a shear force is applied, the PTFE used in the present invention uses P TFE having a molecular weight in the above range. Do. The preferred weight average molecular weight is 600 or more, particularly 5,000 or more, and 500,000 or less, preferably 200,000 or less, more preferably 12,000 or less.

The average particle diameter is preferably in the range of not less than 0.05 m and not more than 10 m. The average particle size is preferably 0.1 m or more, more preferably 0.2 m or more, particularly preferably 1 m or more, and preferably 7 xm or less, more preferably 5 / m or less. When the average particle size is larger than the above range, the dispersion becomes squeezed, but the lubricity of the coating film surface is not improved, and when it is smaller, uniform dispersion becomes difficult.

Furthermore, PTFE may be a homopolymer of tetrafluoroethylene (TFE), or may be a modified PTFE modified with a known modifier (in the present invention, both are collectively referred to as PTFE). . Examples of the modifier include known perfluorovinylether and the like, and the modification amount is preferably up to 1% by weight.

Commercially available products of the PTFE particles (B) include, for example, Lubron manufactured by Daikin Industries, Ltd., Cephralullab manufactured by Central Glass Co., Ltd., and the like.

The compounding amount of the PTFE particles (B) is 50 parts by weight or more, preferably 100 parts by weight or more, particularly 150 parts by weight or more, and 400 parts by weight or less with respect to 100 parts by weight of the water repellent binder resin (A). , Preferably 300 parts by weight, in particular 250 parts by weight or less. If the blending amount is too large, the dispersibility will be poor, and if too small, the blending effect can not be obtained.

(C) Dispersant

Uniformly disperse PTFE particles (B) in the water repellent binder resin (A) Have an effect. The dispersant used in the present invention is not limited to the action of dispersing the PTFE particles (B) in a solvent, for example, when a solvent is used, and the PTFE particles (B) are dispersed uniformly in the water repellent binder resin in the coating film. It is necessary to have an action to Therefore, a suitable dispersant is selected in consideration of the type of the PTFE particles (B) and the water repellent binder-resin (A), and further the type of solvent (if used). When a solvent is not used, for example, when preparing a powder coating, components (A) and (B) may be taken into consideration. When a fluororesin is selected as the water repellent binder (A) and an organic solvent is selected as the solvent (E) described later, a polymer containing a repeating unit derived from a vinyl monomer having a fluoroalkyl group as the dispersant (C (C) 1) is preferred. More preferably, a copolymer of a vinyl monomer having a fluoroalkyl group and a non-fluorinated pinyl monomer is mentioned.

The vinyl monomer having a fluoroalkyl group may be a fluoroalkyl group-containing (meth) acrylate, and the fluoroalkyl group-containing (meth) acrylate may be represented by the following general formula.

R f -A ¹ 10 C (=)) CB ¹ = CH ₂

(Wherein R ί is a fluoroalkyl group having ^{1 to} 21 carbon atoms, Β ¹ is hydrogen or a methyl group, and は¹ is a divalent organic group).

As the fluoroalkyl group-containing (meth) acrylate which is not limited, for example, the following can be exemplified.

Rf- (C3⁄4) _n OCOCI ^ = CH ₂ R ¹

Rf-CO-N OCOCR ³ = CH, OH

Rf-CH ₂ CHCH ₂ OCOCR ³ = CH ₂

OCOR ³

Rf-CH ₂ CHCH ₂ OCOCR ³ = CH ₂

Rf-0-Ar-CH ₂ OCOCR ³ = CH ₂

(Wherein R ¹ is a fluoroalkyl group having 1 to 21 carbon atoms, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is an alkylene group having 1 to 10 carbon atoms, R ³ is hydrogen or a methyl group, Ar is an arylene group which may have a substituent, and n is an integer of 1 to 10.)

Specific examples of the fluoroalkyl group-containing (meth) acrylate which is not limited are shown below.

CF ₃ (CH ₂ ) OCOCH = CH ₂ ,

CF ₃ CF ₂ (CH ₂ ) OCOCH = CH ₂ ,

_{_{_{CF 3 (CF 2) 3 (}}} CH 2) OCOCH = CH 2,

CF ₃ (CF ₂ ) ₄ (CH ₂ ) OC〇CH = CH ₂ ,

CF ₃ (CF ₂ ) ₅ (CH ₂ ) OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₆ (CH ₂ ) CO COCH = CH ₂ ,

CF ₃ (CF ₂ ) ₇ (CH ₂ ) OC〇CH = CH ₂ ,

CF ₃ (CH ₂ ) ₂₀₀ C〇CH = CH ₂ ,

CF ₃ CF ₂ (CH ₂ ) ₂ CC CHCH = CH ₂ ,

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ OCOCH = CH ₂

CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ , CF CF ₂ ) ₇ (CH ₂ ) ₂ OCOCHOCHCH ₂ ,

CF CH ₂ ) ₃ OC〇CH = CH ₂ ,

CF CF, (CH. ₉ 2)

CF ₃ CF ₂ ) ₃ (CH ₂ ) ₃ CC CHCH = CH ₂ ,

CF ₃ CF ₂ ) ₄ (CH ₂ ) ₃ OCOCH = CH ₂ ,

CF ₃ CF ₂ ) ₅ (CH ₂ ) ₃ OC〇CH = CH ₂ ,

CF ₃ CF ₂ ) ₆ (CH ₂ ) ₃ CC CHCH = CH ₂ ,

CF ₃ CF ₂ ) ₇ (CH ₂ ) ₃ OC〇CH = CH ₂ ,

CF, CH ₂ ) ₆ OCOCH = CH ₂ ,

_{_{_{? CF s CF (CH 2)}}} 6 OCOCH = CH;

CF CF ₂ ) ₃ (CH ₂ ) _{6 0} COCH = CH ₂ ,

CF CF ₂ ) ₄ (CH ₂ ) ₆ OC〇CH = CH ₂ ,

CF CF ₂ ) ₅ (CH ₂ ) ₆ OC〇CH = CH ₂ ,

CF CF ₂ ) ₆ (CH ₂ ) ₆ OC〇CH = CH ₂ ,

CF CF ₂ ) ₇ (CH ₂ ) ₆ OCOCH = CH ₂ ,

CF ₃ CH = CHCH ₂ CC〇CH = CH ₂ ,

CF ₃ CF ₂ CH = CHCH ₂ CC〇CH = CH ₂ , CF ₃ (CF ₂ ) ₃ CH = CHCH ₂ OCOCH CHCH ₂ , CF ₃ (CF ₂ ) ₄ CH = CHCH ₂ CC〇CH = CH ₂ , CF ₃ (CF ₂ ) ₅ CH = CHCH ₂ OC〇CH = CH ₂ , CF ₃ (CF ₂ ) ₆ CH = CHCH ₂ OC〇CH = CH ₂ , CF ₃ (CF ₂ ) ₇ CH = CHCH ₂ OCOCH = CH ₂ , (CF ₃ ) ₂ CF (CH ₂ ) ₂ OCOCH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) (CH ₂ ) ₂ OCOCH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ (CH ₂ ) ₂ OCOCH CH CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ COCOCH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₂ OC〇CH = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOCH = CH ₂ , H (CF ₂ ) (CH ₂ ) OCCHCH = CH ₂ ,

_{_{H (CF 2) 2 (CH}} 2) OC_〇_CH = CH _2,

_{_{H (CF 2) 4 (CH}} 2) OCOCH = CH 2,

H (CF ₂ ) ₆ (CH ₂ ) 〇CCCH = CH ₂ ,

_{_{H (CF 2) 8 (CH}} 2) OCOCH = CH 2,

CF ₃ CHFCF ₂ (CH ₂ ) 〇CCCHCHCH ₂ ,

CF ₃ (CH ₂ ) CO COC (CH ₃ ) = CH ₂ ,

CF ₃ CF ₂ (CH ₂ ) OC〇C (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₃ (CH ₂ ) CO COC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ ) OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) CO COC (CH ₃ ) = CH ₂ , CF ₃ (CH ₂ ) OCOCH = CH ₂ ,

CF ₃ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,

_{_{_{CF 3 CF 2 (CH 2)}}} 2 〇_C_〇_C (CH ₃₎ = CH _2,

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ C C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ CO COC (CH ₃ ) = CH ₂ , CF ₃ (CF ₃ ₂ ) ₅ (CH ₂ ) ₂ OC〇C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ CC〇C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) _{2 0} COC (CH ₃ ) = CH ₂ , CF ₃ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH ₂ ,

CF ₃ CF ₂ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₃ CO COC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₃ OC〇C (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ OCOC (CH ₃ ) = CH ₂ ,

CF ₃ (CH ₂₎ ₆ 〇_COC (CH ₃₎ = CH _2,

CF ₃ CF ₂ (CH ₂ ) ₆ o C o C (CI-I ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₆ CO COC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₆ o C o C (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₆ OCOC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₆ CO COC (CH ₃ ) = CH ₂ ,

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₆ OC〇C (CH ₃ ) = CH ₂ ,

CF ₃ CH = CHCH ₂ CC〇C (CH ₃ ) = CH ₂ ,

CF ₃ CF ₂ CH = CHCH ₂ OC〇C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₃ CH = CHCH ₂ OC〇C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₄ CH = CHCH ₂ C COC (CH ₃ ) CH CH ₂ , CF ₃ (CF ₂ ) ₅ CH OC CHCH ₂ OCOC (CH ₃ ) CH CH ₂ , CF ₃ (CF ₂ ) ₆ CH CH CHCH ₂ C C C C (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ CH = CHCH ₂ CC〇C (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₂ (CH ₂ ) ₂ COC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₃ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , _{_{H (CF 2) (CH 2}} ) OCOC (CH 3) = CH 2,

H (CF ₂ ) ₂ (CH ₂ ) CO COC (CH ₃ ) = CH ₂ ,

_{_{H (CF 2) 4 (CH}} 2) 〇_C_〇_C (CH ₃₎ = CH _2,

_{_{H (CF 2) 6 (CH}} 2) 〇_C_〇_C (CH ₃₎ = CH _2,

H (CF ₂ ) ₈ (CH ₂ ) CO COC (CH ₃ ) = CH ₂ ,

CF ₃ CHFCF ₂ (CH ₂ ) OCOC (CH ₃ ) = CH ₂ ,

CF ₃ S _{2 2} N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) S N ₂ N (CH ₃ ) (CH ₂ ) ₂ CO COCH = CH ₂ ,

CF ₃ (CF ₂ ) ₂ S 0 ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₃ S〇 ₂ N (CH ₃ ) (CH ₂ ) ₂ OCHCH = CH ₂ ,

CF ₃ (CF ₂ ) ₄ S 0 ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₅ S〇 ₂ N (CH ₃ ) (CH ₂ ) ₂ OCOCH = CH ₂ ,

CF ₃ (CF ₂ ) ₆ S 0 ₂ N (CH ₃ ) (CH ₂ ) ₂ CO COCH = CH ₂ ,

CF ₃ (CF ₂ ) ₇ S〇 ₂ N (C ₂ H ₅ ) (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ C ₆ F ₁₀ (CF ₂ ) ₂ SO ₂ N (CH ₃ ) ( CH ₂ ) ₂ OC〇CH = CH ₂ , (CF ₃ ) ₂ CFCH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) CH ₂ CH (OCOCH ₃₎ ) CH ₂ OCOC (CH ₃ ) = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH (OCOCH ₃ ) CH ₂ CC〇C (CH ₃ ) = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ >

(CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OCOCH ₃ ) CH ₂ OCOC (CH ₃ ) = CH ₂ ,

(CF ₃ ) ₂ CFCH ₂ CH (〇H) CH ₂ OCCHCH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) CH ₂ CH (OH) CH ₂ OC〇CH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ 0 C〇 CH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₃ CH ₂ CH (OH) CH ₂ COCOCH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH (〇H) CH ₂ OCCHCH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ CC〇 CH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (〇H) CH ₂ CO COCH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ 0 C〇 CH = CH ₂ ,

(CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ CC〇CHCHCH ₂ ,

C ₈ Fi ₇ -0-^^-CH ₂ 0-COCH = CH ₂ C ₅ Fii-0 to <^^ to CH ₂ 0-COC (CH ₃ ) = CH ₂

C8 Fi 7-0 → ^^-COOCH ₂ CHCH ₂ OCO CH ₃ ) = CH ₂

OH

Of course, the above fluoroalkyl group-containing (meth) acrylate may be used as a mixture of two or more.

Examples of the non-fluorine-containing monomer include (meth) acrylate ester. The (meth) acrylate ester may be an ester of (meth) acrylic acid and an aliphatic alcohol such as a monohydric alcohol or a polyhydric alcohol (eg, a dihydric alcohol).

As the non-fluorinated monomer, for example, the following can be exemplified.

2) Ethyl hexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyoxyalkylene (meth) acrylate, alkoxy polyoxyalkylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) Acrylates, N, N-dimethylaminoethyl (meth) acrylate, Ν, Ν-diethylamino (meth) acrylate, benzyl (meth) acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate To, 2-hydroxy-1-hydroxypropyl acrylate, 2-hydroxyacrylate, glycerol monomethacrylate, β ァ -acryloyloxyethyl succinate, i3-methacryloyloxy succinate Chilha Idrogen phthalate, 2-Acrylolic xylethyl oxahydrophthalic acid, 2-Acryloyl xylethyl phthalate, 2-Acryloyloxyethyl 2-Hydroxy xylethyl phthalate, Methoxypropyl trimethyl trimethyl ammonium chloride, Dimethyl amino acid Ethyl methacrylate, Gethylaminocetyl methacrylate, 2-Acryloyloxyethyl phosphite, Dalkosylated mesylate, Methacrylamide, 2-Hydroxy 3-I-acryloyloxypropyl methacrylate, 2 -(Meth) acrylates such as methacrylo xyl oxy acid phosphate, neopentyl dihydroxypivalate and the like; styrenes such as styrene and p-isopropylstyrene; (meth) acrylic acid De, Jiaseto down (meth) acrylamide, N- methylol (meth) acrylamide, N- butoxide -thieno acrylamide, (meth) acrylamides such as 2-acrylamido-2-methylpropane sulfonic acid; vinyl ethers such as vinyl alkyl ether.

Furthermore, ethylene, butadiene, vinyl acetate, vinyl chloride, vinyl chloride such as vinyl chloride, vinyl chloride, vinylidene halide, acrylonitrile, Examples include vinyl alkyl ketone, maleic anhydride, N-vinylcarbazole, vinyl pyrrolidone, (meth) acrylic acid and the like.

Further, the non-fluorinated monomer may be a gayone-based monomer (for example, (meth) acryloyl group-containing alkylsilane, (meth) acryloyl group-containing alkoxysilane, (meth) acryloyl group-containing polyoxysilane). . The polymer (C 1) can be produced by radical polymerization.

The weight average molecular weight of the polymer (C 1) is relatively small and is at least 3,000, more preferably 5,000 or more, particularly 7,000 or more, and 30,000 or less, further 20,000 In the following, it is particularly preferable to be 15, 000 or less.

The compounding amount of the dispersant (C) is 5 parts by weight or more, 10 parts by weight or more, particularly 20 parts by weight or more, 100 parts by weight or less, per 100 parts by weight of the water repellent binder resin (A). Furthermore, it is preferably 80 parts by weight or less, particularly 60 or less.

In the present invention, particles (D) and / or a solvent (E) of low heat capacity can be added if necessary. I will explain below.

(D) low heat capacity particles

When blending particles (D) with low heat capacity, the reason is unknown, but with or without water repellence the slipperiness is further improved. It can also be expected to facilitate deicing (snow) in the event of icing (snow).

The heat capacity of the particles (D), 30 C a / J K_ 1 one ¹ in terms of a molar heat capacity, particularly preferably 7 Ca / JK I- ¹ below. The lower limit is usually 6Ca ZJK 1 ¹ mo 1 ¹

As such low heat capacity particles, particles of many metals or nonmetals alone, and further, particles of some metal compounds are applicable. Specific examples include metals such as gold, silver, aluminum, iron and copper; nonmetals such as carbon and boron; Other metal compounds may be mentioned.

From another point of view, it is desirable that the low heat capacity particles (D) be electrically conductive. Most of the water repellent binders are chargeable, and it is easy to attach dust that becomes an ice core on the surface of the coating, so that it is possible to further prevent icing (snow) by preventing the surface of the coating from being charged.

Furthermore, in order not to impair the weather resistance, it is desirable that the low heat capacity particles also have high weather resistance, corrosion resistance, and solvent resistance.

From the above viewpoints, carbon black which is a simple substance of carbon, particularly crystalline carbon black is particularly preferable.

The average particle size of the low heat capacity particles (D) is preferably 2 z m or more and 12 m or less from the viewpoint of dispersibility.

The compounding amount of the low heat capacity particles (D) is 25 parts by weight or more, further 40 parts by weight or more, particularly 60 parts by weight or more, with respect to the water repellent binder resin (A) 100 parts by weight, The content is preferably 400 parts by weight or less, more preferably 200 parts by weight or less, and particularly preferably 150 parts by weight or less.

(E) Solvent The solvent (E) facilitates uniform mixing of the surface treatment composition of the present invention, facilitates formation of a coating film, and further uniformly disperses various components in the water repellent binder resin. It is useful. Thus, the solvent (E) is selected taking into account the other components (A), (B), (C) and, if formulated, the component (D). The solvent (E) may be an inorganic solvent such as water, but an organic solvent is preferable from the above viewpoint. The organic solvent system may be a single solvent or a mixture of two or more solvents. When two or more kinds are used, it is desirable to include a polar organic solvent and a nonpolar organic solvent from the viewpoint of more uniformly dispersing the other components. Examples of polar organic solvents include, for example, butyl acetate, ethyl acetate, acetone,, ethanol, isopropanol, butanol, Ethylene glycol monoalkyl ether etc. are mentioned.

Examples of nonpolar organic solvents include toluene, xylene, n-hexane, cyclohexane and heptane, as well as petroleum spirits such as terpene.

In particular, by mixing and using butyl acetate and a petroleum solvent (toluene, xylene, n-hexane, cyclohexane, heptane, water pen, etc.), the sliding property (slip angle) of the resulting coating film is adjusted it can. The mixing ratio is optional depending on the type of solvent to be combined, but the same weight or a large amount of butyl acetate is preferable from the viewpoint of good lubricity.

(F) Crosslinking agent

In applications where solar panels are covered with heat, such as a solar panel cover, and the icing and deicing cycles are repeated due to differences in sunshine, it is desirable to increase the strength of the coating and maintain the sliding property over a long period of time. For that purpose, it is desirable to crosslink the resin. Crosslinking can be achieved by irradiation with high energy radiation etc. without using a crosslinking agent, but using a resin having a chemically curable reactive group as binder resin (A) and blending a crosslinking agent Is preferred.

Examples of the binder resin having a chemically curable reactive group include silicone resins having a chemically curable reactive group in addition to the fluorine resin having a chemically curable reactive group described above, a polyester resin, and a polyolefin. Resin, acrylic resin, polyurethane resin, etc. may be mentioned, but it is not limited thereto.

The crosslinking agent may be any one that reacts with the curing reactive group of the resin having the curing reactive group to cure the resin. For example, an isocyanate compound, an amino resin, an acid anhydride, a polysilane compound, a polyepoxy compound, Isocyanate group-containing silane compounds are usually used.

As isocyanato compounds, for example, 2, 4-tolylene diisocyanate , Diphenylmethane diisocyanate, xylylene diisocyanate, methylcyclohexyldiisosylate, trimethylhexamethylene diisocyanate, hexamethylenediisosylate, n-pentanone, 1,4-diisocyanate, These trimers, adducts or adducts of these adducts, those having two or more isocyanato groups in these polymers, and blocked isocyanatos and the like, but are limited thereto is not.

Examples of amino resins include urea resins, melamine resins, benzoguanamine resins, glycoluril trees, methylolated melamine resins obtained by methylating melamine, methylolated melamines such as methanol, ethanol and butanol, etc. Examples thereof include alkyl etherified melamine resins etherified with alcohols, but not limited thereto.

Examples of the acid anhydride include, but are not limited to, phthalic anhydride, pyromellitic anhydride, and mellittic anhydride.

The polysilane compound is a compound having two or more groups selected from a hydrolyzable group directly bonded to a silicon atom and a S i OH group, or a condensate thereof, as described, for example, in JP-A-2-2322. The compounds described in JP-A-50, JP-A-2-23225 and the like can be used. Specific examples thereof include, for example, dimethyldimethoxysilane, dibutyldimethoxysilane, diisopropyldipoxysilane, diphenyldibutoxysilane, diphenylethoxysilane, jetyldisilanol, dihexyldisilanol, methyltrimethoxysilane, and methyltrimethoxysilane. Ethoxysilane, acetoxylsilane, provirtrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, hexyltriacetoxysilane, methyltrisilanol, phenyltrisilanol, tetramethoxysilane, tetramethoxysilane Examples thereof include diisopropoxydivaleroxysilane and tetrasilane silanol. As the polyepoxy compound or a phosphonate group-containing silane compound, for example, compounds described in JP-A-2-232250 and JP-A-2-232251 can be used. As a preferred embodiment, for example, the following compounds can be exemplified.

N c ccc = ll

CH ₂ — CH — CH ₂ — 0 — C. H H H ₂ CH ₂ — 0 — CH ₂ — CH — CH ₂ ,

2

O 〇

CH, -CH-CH, -N N-CH ₂ -CH-CH.

O C C O

//

O O

\ ○

CH /

CH ₉ -CH-CH,-H ₂ ,

Yes

○ CNC ₃ H ₆ S i ((C ₂ H ₅ ) 3,

OCNC ₂ H ₄ S i (〇CH ₃ ) 3

The compounding amount of the crosslinking agent is not less than 0.1 equivalent, preferably not less than 0.5 equivalent, and not more than 5 equivalents, preferably 1 per equivalent of the curing reactive group in the curing reactive group-containing binder resin. Less than 5 equivalents.

In the present invention, a curing accelerator can also be used. As a hard-ring accelerator, for example, organotin compounds, acidic phosphoric acid esters, acidic phosphoric acid esters The reaction product of a compound with an amine compound, an amine compound, lead octyrate and the like can be mentioned. The curing accelerator may be used alone or in combination of two or more.

The amount of curing accelerator, the binder resin 1 0 0 part by weight, 1. 0 X 1 0- ⁶ parts by weight or more, preferably 5. 0 X 1 0- ⁵ part by weight or more, also 1. 0 X 1 0 one ² parts by weight, preferably not more than 1. 0 X 1 0- ³ parts by weight. The surface treatment composition of the present invention can be prepared in various forms as long as it can form a coating film, but it is preferable to prepare a powder coating or a solvent-type coating from the viewpoint of easy formation of a coating. It is preferable to prepare a solvent type paint.

The composition of the present invention preferably has a solid content concentration of 5 to 40% by weight, particularly 15 to 30% by weight from the viewpoint of paintability and dispersibility. In addition, various additives such as pigments, other resins, flow control agents, anti-coloring agents, antioxidants, UV absorbers and the like may be blended unless the object of the present invention is impaired.

The preparation of the composition for surface treatment as the solvent-based paint of the present invention is carried out by charging each component into the solvent (E) and sufficiently stirring. The stirring method is not particularly limited, but ultrasonic stirring method, forced stirring method and the like are preferable from the viewpoint of being able to easily and uniformly disperse particle components such as PTF E particles (B) and low heat capacity particles (D). The coating method is not particularly limited. For example, methods such as dip coating method, bar coat method, roll coating method, and spray method can be adopted. After application, it is dried at room temperature or, if necessary, dried by heating to form a cured film. The film thickness of the coating film may be appropriately selected depending on the application portion, but is usually 1 or more, further preferably 30 / z m or more, 0.2 mm or less, further preferably 0.1 mm or less.

The substrate to be applied is not particularly limited, and is determined by the equipment, equipment, equipment, parts, etc. which require the prevention of icing (snow). Examples include aluminum, stainless steel, copper, various alloys, and ceramics.

The coating thus obtained has a sliding angle (4-liter water droplet) of less than 15 degrees, Preferably it is 10 degrees or less, more preferably 5 degrees or less. When the sliding angle is close to 0 degree (horizontal), the sliding water is excellent.

From the viewpoint of water repellency, the contact angle to water of the coating film surface is preferably 140 degrees or more, more preferably 145 degrees or more, and particularly preferably 150 degrees or more.

The coating film having such surface characteristics can easily slide down the small water droplets formed on the water repellent surface, and does not form nuclei of icing (snow) and prevents icing (snow). Improve.

The composition for surface treatment of the present invention may be used in equipment, equipment, facilities, structures, or parts thereof which may cause damage or decrease in function due to icing or snow deposition or cause injury to persons. Apply

Specifically, it exerts excellent effects when applied to the following. Various antennas such as parabola antenna; Communication towers; Communication cables; Wires; Transmission towers

Transport vehicle related:

Decks of ships and trains; Steps of getting on and off various vehicles; Pantographs, external projections of vehicles such as railway lines; Wings of aircraft; Exteriors of various vehicles:

Roof tiles, exteriors such as tiles

Other:

Solar panel cover etc

Next, the present invention will be described based on examples, but the present invention is not limited to such examples.

Example 1

Zeffle GK-510 (hereinafter referred to as "binder resin Al") manufactured by Daikin Industries, Ltd. as a water repellent binder resin (A), PTFE particles (B Cefralub (trade name; modified PTFE with an average particle size of 5 to 10 m) manufactured by Central Glass Co., Ltd. Weight average molecular weight 1500 to 20000. Below, referred to as “PTFE particles B 1”, dispersant (C ) Using Yunidyne TG-656 manufactured by Daikin Industries, Ltd., the amount described in Table 1 is added to the organic solvent (E) shown in Table 1 and mixed by ultrasonic agitation method for surface treatment The composition was prepared.

The composition for surface treatment obtained is applied by spray method on an aluminum plate (A1 200 series of JI SH4000. 10 OmmX 10 Omm), left to stand at room temperature for 1 day for hardening, and then the coated film surface is removed. Do not wash but dry and test plate

(Film thickness 20 zm) was produced.

The coated plate was checked for contact angle to water and sliding angle (4 liters) by the following method. The results are shown in Table 1.

(Measurement of contact angle to water)

According to J I SR 3257, it is measured at a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70% using a contact angle meter (CA-VP, trade name) manufactured by Kyowa Interface Science Co., Ltd. The larger the angle, the higher the water repellency.

(Slip angle measurement method)

A sample placed horizontally on a contact angle meter (CA-VP, trade name) manufactured by Kyowa Interface Science Co., Ltd. and placed horizontally in an environment with a relative humidity of 60 ± 2% at a temperature of 17 ± 1. Drop 4 liters of distilled water onto the plate to form a water droplet, and then tilt the sample plate at an angle of 0.1 degrees, and measure the angle of the sample plate when the water droplet starts rolling. The measurement shown in the table is the initial sliding angle. The smaller the angle, the better the water drop (water slip).

Surface treatment composition (parts by weight) Sliding angle (degree)

Water contact angle

Experiment number Component)

Component (A1) Component (B1) Component (C) (Degree) ΙΟμΙ 4μ1

Butyl acetate hexane heptane

1-1 4.0 4.0 4.0 4.0 154. 2 9. 2 12.0

O

1— 2 4.0 4.0 4.0 14.0 6.0 154. 3 6.0

1-3 4.0 4.0 4.0 12.0 ○ 8.0 153.2

0O 0 L Example 2

In Example 1, the compounding ratio of the components (A), (B), (C) and (E) is the ratio shown in Table 2, and the particles shown in Table 2 as low heat capacity particles (D) are also shown in the same table. A surface treatment composition was prepared and painted in the same manner as in Example 1 except that the amount shown in was added, to prepare a coated plate for testing. The stirring method was ultrasonic stirring.

With respect to this coated plate, the contact angle to water and the sliding angle were examined in the same manner as in Example 1. The results are shown in Table 2.

The low heat capacity particles in Table 2 are as follows.

CBD 1: Forced Bon black particles D 1 (manufactured by Sigma Aldrich. Average particle size 2 to 12 x m)

GF: natural graphite (average particle size about 3 m)

Table 2 Composition for surface treatment (parts by weight)

Component (D) Component Water contact angle ■ Bone angle (J ^)

Experiment number

Component (A1) Component (B1) Component (C) (degree)

Type-g.

Village butyl acetate heptane 4 μ 1

2–1 4. 0 2. 0 2. 0 GF 2.0

154. 9 8. 7

2- 2 4. 0 4. 0 4. 0 CBD 1 2. 0 152. 1 4. 6

2-3 4. 0 4. 0 4. 0 GF 0.5 5.

C

0

2-4 4. 0 4. 0 4. 0 GF 0.5 20. 0 20. 0 150. 9 12. 2

2-5 4. 0 4. 0 4. 0 GF 0.5 0 0 0 0 0 154. 1 10. 9

2-6 4. 0 2. 0 2. 0 GF 0. 5 20. 0 20. 0 152. 8 9. 9

2-7 4. 0 2. 0 2. 0 GF 0.5 28. 0 150. 5

2-8 4. 0 4. 0 4. 0 GF 2. 0 20. 0 156. 4 5. 8

CO Ο 〇〇

o

Lili

o

6Ο

Lili

O Example 3

In experimental example 2-2 of Example 2 (carbon black particles D 1) and experimental example 2-18 (natural graphite particles), the obtained coating was cured by heating at 120 for 10 hours, and a coated plate for testing was used. Was produced.

The contact angle to water and the sliding angle of the heat-cured coated sheet were examined in the same manner as in Example 1. The results are shown in Table 3.

Table 3 Composition for surface treatment (parts by weight) Sliding angle (degree)

Water contact angle

备) 3⁄4 component (D) component)

Component (A1) Component (B1) Component (C) (degree) 10 μm

Kind

Village butyl acetate heptane

C

o

3-1 4. 0 4. 0 4. 0 CBD 1 2. 0 20. 0 20. 0 155. 5 4. 2 8. 3

3-2 4. 0 4. 0 4. 0 GF 2. 0 20.0 20. 0 154 10. 3 12. 3

Example 4

In Experiment No. 2-2 of Example 2, the same applies except that Lubron L-5 (hereinafter referred to as "PT FE particle 2") manufactured by Daikin Industries, Ltd., which is a low molecular weight P TFE particle, is used as the PTFE particle. Then, a composition for surface treatment was prepared, applied as in Example 1, and the obtained coating was allowed to stand at room temperature for 24 hours to prepare a coated plate for a test.

The contact angle to water and the sliding angle (4 liters) of this coated plate were examined in the same manner as in Example 1. In addition, we also investigated the sliding angle of ultra-fine water droplets (1 liter). The results are shown in Table 4 together with Experiment No. 2-2 of Example 2.

(Ultrafine water droplet sliding angle measurement method)

The coated plate is horizontally fixed to a contact angle meter (CA-VP, trade name) manufactured by Kyowa Interface Science Co., Ltd., and placed horizontally under an environment of 60% soil and 2% relative humidity at a temperature of 17 ± 1 ° C. Dispense distilled water onto the sample plate by 1 μl drop using a pneumatically driven air-operated syringe (Ultra-small application needle valve 740MD-SS. Trade name from EDF, USA) to form water droplets, and then form a water droplet, and then the sample plate at an angle of 0.1. Tilt it by degrees and measure the angle of the sample plate when the water drop begins to roll. The measured values shown in the table are the initial ultrafine water droplet sliding angle. The smaller the angle, the better the ultra-fine water droplet sliding property (water sliding property).

Example 5

In Experimental Example 2- of Example 1, a VdFZ TFE copolymer (Zuffel LC 1 930, manufactured by Daikin Industries, Ltd.) having no chemically curable reactive group as a binder resin is used. A composition for surface treatment was prepared in the same manner as in the resin A2), and applied as in Example 1. The resulting coating was allowed to stand at room temperature for 24 hours to give a coated plate for testing. It was made.

For this coated plate, the contact angle to water and the sliding angle (4 liters) were used as an example. The ultrafine water droplet sliding angle was examined in the same manner as in Example 1 in the same manner as in 1. The results are shown in Table 4.

Example 6

In Experimental Example 2-2 of Example 2, 3.2 (parts by weight) and 0.8 parts by weight of A 1 (Zeffer GK-510) and A 2 (Zeffle LC-930) were used as binder resins, respectively. A surface treating composition was prepared in the same manner as in Example 1 and was applied as in Example 1. The resulting coated film was left at room temperature for 24 hours to prepare a coated plate for testing.

With respect to this coated plate, the contact angle to water and the sliding angle (4 liters) were examined in the same manner as in Example 1, and the sliding angle for ultra-fine water droplets was further examined in the same manner as in Example 4. The results are shown in Table 4.

Example 7

In Experimental Example 2-2 of Example 2, the surface is the same as in Example 2 except that # 3 230 B (hereinafter referred to as “carbon black particle D 2”) manufactured by Mitsubishi Chemical Co., Ltd. is used as carbon black particles. A treatment composition was prepared, applied as in Example 2, and the obtained coating was allowed to stand at room temperature for 24 hours to prepare a test board.

With respect to this coated plate, the ultrafine water droplet sliding angle was examined in the same manner as in Example 4 in the same manner as in Reference Example 1 with respect to the water contact angle and sliding angle (liter). The results are shown in Table 4. Table 4 Composition for surface treatment (parts by weight)

Contact angle to water Slip angle (degree) Example Component (A) Component (B) Component (D)

Component (C) Component) (degree)

s 1 4 μ 1 1 β \ Example 2

A1 4.0 B1 4. 0 4.0 CBD 1 2. 0 40. 0 157. 7 4. 0 7.5 (Experimental example 2-2)

Example 4 A1 4.0 B2 4. 0 CBD1 2. 0 40. 0 157. 0 7. 4 7. 8 Example 5 A2 4.0 B1 4.0 0 CBD 1 2. 0 40. 0 156. 2 5. 4 5. 7 Example 6 A1 + A2 2. 0 + 2. 0 B1 4. 0 4. 0 CBD 1 2. 0 40. 0 157. 4 1. 5 2. 8 Example 7 A1 4. 0 B1 4. 0 4. 0 CBD 2 2. 0 40. 0 157. 7 4. 3 4. 6

Example 8

Binder resin A 1 (Zeffle GK-510) containing a chemically curable reactive group as water repellent binder resin (A), PTFE particle B 1 (Cefral loop) as PTFE particles (B), dispersant (C) As unidine T G 656, low heat capacity particles (D), carbon black particles D 1 as a crosslinker (F), deyuranate 24A-100 (isosocyanate crosslinker, trade name) manufactured by Asahi Kasei Co., Ltd. is used. An amount described in Table 5 (the same amount as experimental example 2-2 in Example 2 except for the cross-linking agent) was added to butyl acetate / heptane (1Z1 weight ratio), and was stirred and mixed by ultrasonic agitation method for surface treatment The composition was prepared. The composition for surface treatment obtained was applied by spray method on an aluminum plate (A1 200 series of JI SH4000. 10 OmmX 10 Omm), allowed to stand at room temperature for 24 hours and cured, and then the coated film surface was washed. It was dried without drying to prepare a test plate (film thickness 2 O fim).

With respect to this cured coated plate, the contact angle to water and the sliding angle (4 liters) are made the same as in Example 1, and the sliding angle of ultrafine water droplets is further made in the same manner as in Example 4, and the pencil height is JIS K5600-5-5- 4 (1999). The results are shown in Table 5 together with Experiment No. 2-2 of Example 2.

Table 5 Composition for surface treatment (parts by weight)

Sliding angle (degree) against water contact angle

Example Component) Component (B) Component (D) Hardness

(Every time)

Component (C) Component) Component (F)

Village β β 実施 Example 2

A1 4.0 B1 4. 0 4.0 CBD1 2. 0 40. 0 157. 7 4. 0 7. 5 5 (Experiment No. 2-2) Example 8 A1 4.0 B1 2. 0 4.0 CBD1 2. 0 40. 0 0. 073 157. 9 3.5 3 8 3

Industrial applicability

According to the composition for surface treatment of the present invention, it is possible to uniformly disperse the P T F E fine particles on the surface of the fluorine-containing resin coating film, and furthermore, it is possible to provide a coating film having high water repellency and slipperiness against water droplets. Therefore, the effect of preventing icing and snow is further improved.

Claims

函求範函

1. (A) Water-repellent binder resin,

(B) polytetrafluoroethylene particles, and

(C) Dispersant

What is claimed is: 1. A composition for surface treatment comprising: a composition for surface treatment, wherein a first sliding angle of sliding angle defined below is 15 degrees or less.

Record

(1) 4 liters of distilled water is dropped on a sample plate placed horizontally in an environment with a temperature of 17 ± 1 ° C and a relative humidity of 60 ± 2% to form water droplets, and then the sample plate is Increment the angle by 1 degree, and let the angle of the sample plate when the water drop begins to roll be the sliding angle.

2. 50 parts by weight or more and 400 parts by weight or less of the polytetrafluoroethylene particles (B) per 100 parts by weight of the water-repellent binder resin (A) and 5 parts by weight of the dispersant (C) The composition according to claim 1, which contains 100 parts by weight or less and 10 parts by weight or less.

3. A composition according to claim 1 or 2 further comprising particles (D) of low heat capacity.

4. The water-repellent binder resin (A) according to claim 3, containing 250 parts by weight or more and 400 parts by weight or less of particles (D) of low heat capacity with respect to 100 parts by weight. Composition.

5. The composition according to any one of claims 1 to 4, further comprising a solvent (E).

6. The composition according to claim 5, wherein the solvent is contained in an amount of 400 parts by weight or more and 400 parts by weight or less based on 100 parts by weight of the water-repellent binder resin (A).

7. The water-repellent binder resin (A) is a fluorine resin, The composition according to any one of Items 6 to 6.

8. The fluorine resin is

(1) Formula (I):

One CF ₂ — CFX-(I)

(In the formula, X is a fluorine atom, a chlorine atom, a hydrogen atom or a trifluoromethyl group) Fluoro olef structural unit (1),

(2) Formula (II):

— CH ₂ — CR (CH ₃ ) 一 (II)

(In the formula, R is an alkyl group having 1 to 8 carbon atoms) 3-methyl-substituted fluorofine structural unit (2),

(4) Structural units based on a monomer having an ester group in the side chain (4), and

(5) Structural units based on other copolymerizable monomers (5)

Consisting of 20 to 60 mol% of structural unit (1), 5 to 25 mol% of structural unit (2), 1 to 45 mol% of structural unit (3), and 1 to 45 mol% of structural unit (4) And a structural unit (5) containing 0 to 45 mol% (wherein the total of structural units (1) + (2) is 40 to 90 mol%) a fluorine-containing co-weight having a number average molecular weight of 1000 to 500000 A composition according to claim 7 which is coalesced.

9. The composition according to any one of claims 1 to 8, wherein the polytetrafluoroethylene particles (B) have an average particle size in the range of 1 m to 10 m.

10. The composition according to any one of claims 1 to 9, wherein the polytetrafluoroethylene particles (B) have a weight average molecular weight in the range of 500 to 500,000.

11. The composition according to any one of claims 1 to 10, wherein the polytetrafluoroethylene particles (B) have a weight average molecular weight in the range of 500 to 20, 000. object.

12. The composition according to any one of claims 1 to 11, wherein the dispersant (C) is a polymer comprising a repeating unit derived from a vinyl monomer having a fluoroalkyl group.

13. The composition according to claim 12, wherein the polymer is a copolymer with a non-fluorinated vinyl monomer.

14. The composition according to any one of claims 3 to 13, wherein the particles (D) of low heat capacity are particles having a molar heat capacity of 3 0 C a ZJK ^ mo 1 ¹ or less.

15. The composition according to any one of claims 3 to 14, wherein the particles (D) of low heat capacity have an average particle size in the range of 2 x m to 12.

16. The composition according to any one of claims 3 to 15, wherein the particles (D) of low heat capacity are strong carbon black particles.

17. A composition according to claim 16 wherein the carbon black particles are crystalline force pump rack particles.

18. The composition according to any one of claims 5 to 17, wherein the solvent (E) is an organic solvent system.

19. The composition according to claim 18, wherein the organic solvent system is a solvent system in which two or more organic solvents are present.

20. The composition according to claim 18, wherein the organic solvent system is a solvent system comprising a polar organic solvent and a nonpolar organic solvent.

21. The composition according to any of claims 1 to 20 in the form of a paint.

22. A binder resin (A) further containing a crosslinking agent (F) and having water repellency is preferred. The composition according to any one of claims 1 to 21, which is a resin having a chemical curing reactive group.

23. The curing agent (F 1) according to claim 1, which contains 0.1 equivalent or more and 5 equivalents or less of the crosslinking agent (F) with respect to 1 equivalent of the chemical curing reactive group in the water repellant binder resin having the chemical curing reactive group. 2. The composition according to item 2 above.

24. The composition according to any one of claims 1 to 23, wherein a coating film having an initial micro water droplet sliding angle of not more than 15 degrees is provided, as defined below.

Record

(2) 1 // liter of distilled water is dropped on a sample plate placed horizontally in an environment with a temperature of 17. ± .1 and a relative humidity of 60 ± 2% to form water droplets, and then the sample plate is The angle is 0.1 degree. The angle of the sample plate when the water drop begins to roll is the sliding angle of the ultra-small water drop.