JP2015075290A - Antifouling composition for exhaust duct, grease filter, or range hood, antifouling film for exhaust duct, grease filter, or range hood, exhaust duct, grease filter, and range hood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling composition for an exhaust duct, a grease filter, or a range hood capable of suppressing fouling by grease and the like, and making the fouling easily removed, an antifouling film for the exhaust duct, the grease filter, or the range hood, and the exhaust duct, the grease filter, and the range hood which is prevented from being fouled by grease and the like, and from which the fouling can be easily removed.SOLUTION: An antifouling composition for an exhaust duct, a grease filter, or a range hood, and an antifouling film for the exhaust duct, the grease filter, or the range hood, include a fluorine resin (A) including a functional group X. The exhaust duct, the grease filter, and the range hood are coated with the antifouling composition or provided with the antifouling film.

Description

The present invention relates to an exhaust duct, a grease filter or an antifouling composition for a range hood, an exhaust duct, an grease filter or an antifouling film for a range hood, an exhaust duct, a grease filter, and a range hood.

Smoke generated by the use of cooking utensils such as a gas stove in the kitchen contains oil, fat, dust, odor components, etc., and is usually filtered by a grease filter installed in front of the intake port of the exhaust duct. It is exhausted outside through the exhaust port.

If the grease filter is allowed to stand for a long period of time, the oil or the like adheres and accumulates, and the performance of the grease filter decreases. If the performance of the grease filter deteriorates, the exhaust gas enters the exhaust duct without sufficient removal of oil and fat in the exhaust gas, contaminates the exhaust duct, or contains oil and fat. There arises a problem that the flue gas is exhausted to the outside. Therefore, periodic cleaning of the grease filter, the range hood that surrounds it, and the exhaust duct is indispensable. Failure to do so may cause a fire.

On the other hand, the cleaning work inside the exhaust duct must be carried out after the exhaust duct is removed by the worker, or when the exhaust duct cannot be removed. It becomes.

Conventionally, various devices for effectively removing oils and fats, dust, odor components and the like contained in the flue gas in the kitchen have been studied (for example, see Patent Documents 1 and 2), but on-site removal work. There has been a demand for a means to further improve the efficiency.

JP 2003-336876 A JP 2009-222292 A

The object of the present invention is, in view of the above-mentioned present situation, is difficult to get dirt such as oils and fats, exhaust ducts, grease filters and range hoods that are easy to remove dirt, and dirt such as oils and fats, An object of the present invention is to provide an antifouling composition and an antifouling film that facilitate removal of dirt in an exhaust duct, a grease filter, and a range hood.

The present invention is an antifouling composition for an exhaust duct, a grease filter or a range hood containing a fluororesin (A) containing a functional group X. Hereinafter, this is also referred to as “the antifouling composition of the present invention”.

The present invention is also an antifouling film for exhaust ducts composed of a film formed from the antifouling composition for exhaust ducts, and an antifouling film for grease filters composed of a film formed from the antifouling composition for grease filters. There is also an antifouling film for range hoods comprising a film formed from the antifouling composition for range hoods. The present invention is also an antifouling film for exhaust ducts comprising a coating film formed from the antifouling composition for exhaust ducts and an adhesive layer, and a coating formed from the antifouling composition for grease filters. It is also an antifouling film for grease filters comprising a membrane and an adhesive layer, and is also an antifouling film for range hoods comprising a coating film formed from the antifouling composition for range hoods and an adhesive layer. Furthermore, the present invention is also an antifouling film for exhaust ducts comprising a coating film formed from the antifouling composition for exhaust ducts and a layer formed from a non-fluorinated polymer, and the antifouling composition for grease filters. An antifouling film for a grease filter comprising a coating film formed from a product and a layer formed from a non-fluorinated polymer, the coating film formed from the antifouling composition for a range hood, and a non-fluorinated polymer It is also an antifouling film for a range hood including a layer formed from Hereinafter, these are collectively referred to as “antifouling film of the present invention”.

The present invention is also an exhaust duct to which the antifouling composition for exhaust duct is applied, and an exhaust duct to which the antifouling film for exhaust duct is attached. Hereinafter, these are collectively referred to as “the exhaust duct of the present invention”.

The present invention is also a grease filter coated with the antifouling composition for grease filter, and a grease filter to which the antifouling film for grease filter is attached. Hereinafter, these are collectively referred to as “the grease filter of the present invention”.

The present invention is also a range hood to which the antifouling composition for a range hood is applied and a range hood to which the antifouling film for the range hood is attached. Hereinafter, these are collectively referred to as “the range hood of the present invention”.

First, the antifouling composition of the present invention will be described.

The antifouling composition of the present invention contains a fluororesin (A) containing a functional group X. The functional group X of the fluororesin (A) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a carbonyl group, a nitrile group, and a hydrolyzable alkyl silicate residue. It is preferable that

The antifouling composition of the present invention preferably further contains an antifouling component (B). The antifouling component (B) is preferably at least one component selected from the group consisting of a liquid polydialkylsiloxane (B1) and a liquid fluoropolyether (B2).

The polydialkylsiloxane (B1) has a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a thiol group, — (C ₂ H ₄ O) _a — (C ₃ H ₆ O) _b R ¹ (R ¹ is the number of carbon atoms) Represents an alkyl group of 1 to 8. a and b are the same or different and each represents an integer of 1 to 40.), and at least one selected from the group consisting of hydrolyzable alkyl silicate residues One of it is preferable to contain a functional group Y ^1.

The fluoropolyether (B2) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a thiol group, a nitrile group, an iodine atom, and a hydrolyzable alkyl silicate residue. preferably contains Y ^2.

The antifouling composition of the present invention preferably further contains a curing agent (C). Further, the curing agent (C), an isocyanate compound, amino compound, epoxy compound, organic acid, hydrazide compound, aziridine compound, carbodiimide _{^{compound, -Si (OR 4) 4 (}} R 4 is a non having 1 to 10 carbon atoms represents a fluorinated hydrocarbon group.) compounds _{^{containing, R 5 Si (oR 4)}} 4 (R 5 and ^{R 6} are the same or different and each represents a non-fluorinated hydrocarbon group having 1 to 10 carbon atoms. ) -Containing compounds, single condensation oligomers thereof, and at least one compound selected from the group consisting of these co-condensation oligomers.

The curing agent (C) is used to bind the fluororesin (A) and the antifouling component (B), but only with the fluororesin (A) and the antifouling component (B). If this occurs, it is not always necessary.

Next, the antifouling film of the present invention will be described.

The antifouling film of the present invention comprises (a) a single layer film comprising a coating film formed from the above antifouling composition, (b) a coating film formed from the above antifouling composition, and a non-fluorinated polymer. And a laminated film including the formed layer.

The coating film may be a film obtained by applying an antifouling composition to a release substrate, drying or curing the film, and then peeling it off from the release substrate. The laminated film (b) is further composed of (b1) a laminated film in which the coating film and a layer formed from the non-fluorinated polymer are directly overlapped, and (b2) the coated film and the non-fluorinated polymer. The formed layer is divided into a laminated film with an adhesive layer interposed therebetween. For each of these films, an adhesive layer may be provided in advance on the surface to be attached to the exhaust duct, grease filter or range hood.

Next, the exhaust duct, grease filter and range hood of the present invention will be described.

The exhaust duct of the present invention is coated with the antifouling composition for exhaust ducts or attached with the antifouling film for exhaust ducts. Moreover, application | coating of the said antifouling composition for grease filters, or affixing of the said antifouling film for grease filters is made | formed with respect to the grease filter of this invention. Furthermore, application | coating of the said antifouling composition for range hoods, or the pasting of the said antifouling film for range hoods is made | formed with respect to the range hood of this invention.

According to the antifouling composition of the present invention, when applied to an exhaust duct, a grease filter or a range hood, dirt such as oil and fat is less likely to adhere, and removal of dirt during cleaning is facilitated. According to the antifouling film of the present invention, when attached to an exhaust duct, a grease filter or a range hood, dirt such as oil and fat is less likely to adhere, and removal of dirt during cleaning is facilitated. The exhaust duct, grease filter, and range hood of the present invention are less likely to be contaminated with dirt such as fats and oils, and the dirt can be easily removed during cleaning.

It is a cross-sectional schematic diagram which shows an example of the exhaust duct with which the kitchen was equipped, the grease filter, and the range hood. It is the isometric view schematic diagram which took out the exhaust duct, grease filter, and range hood which were shown in FIG.

The antifouling composition of the present invention can be used by directly applying it to an exhaust duct, a grease filter and a range hood as a paint, but it is also used as a material for producing the antifouling film of the present invention.

The antifouling composition of the present invention is required to contain a fluororesin (A) having a functional group X, and a certain antifouling property can be obtained even with a fluororesin (A) having a functional group X alone. However, the antifouling component (B) and the curing agent (C) are further contained, thereby exhibiting better antifouling properties. In particular, the functional group of the fluororesin (A) and the antifouling component (B) are chemically bonded via the curing agent (C) or directly condensed to obtain the antifouling component (B). Further excellent antifouling property is exhibited by making it unevenly distributed in the vicinity of one surface of the coated film or antifouling film.

Suitable examples of the antifouling component (B) contained in the antifouling composition include liquid polydialkylsiloxane (B1) and liquid fluoropolyether (B2). “Liquid” here means one having fluidity at room temperature (25 ° C.).

First, the polydialkylsiloxane (B1) will be described in detail.

The polydialkylsiloxane (B1) refers to an oligomer in which two or more identical dialkylsiloxanes are condensed, or a co-oligomer in which two or more different dialkylsiloxanes are condensed. The number of dialkylsiloxanes to be condensed is preferably 10 or more. The number of dialkylsiloxanes to be condensed is preferably 10,000 or less, more preferably 1,000 or less.

Polydialkylsiloxane (B1) is, as a functional group ^{Y 1,} hydroxyl group, a carboxyl group, an epoxy group, an amino group, a thiol _{group, - (C 2 H 4 O} ) a - (C 3 H 6 O) b R 1 (R ¹ represents an alkyl group having 1 to 8 carbon atoms, a and b are the same or different and each represents an integer of 1 to 40), and selected from the group consisting of hydrolyzable alkyl silicate residues It is preferable that the compound contains at least one functional group, more preferably 1000 or less.

As the hydrolyzable alkyl silicate residue, —SiR ² _3-m (OR ³ ) _m (wherein R ² represents a non-hydrolyzable hydrocarbon group having 1 to 18 carbon atoms, and part or all of A hydrogen atom may be substituted with a fluorine atom, R ³ represents a hydrocarbon group having 1 to 18 carbon atoms, and m is an integer of 1 to 3). preferable.

Examples of R ² include a methyl group, an ethyl group, and a propyl group.

Examples of R ³ include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable from the viewpoint of excellent hydrolyzability.

m is preferably 3 from the viewpoint of excellent hydrolyzability.

As the functional group ^{Y 1} containing polydialkylsiloxane (B1), specifically, the following formula (1):

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same or different and each represents an alkyl group having 1 to 8 carbon atoms, an Rf group (the Rf group is linear or branched) Or a functional group Y ¹ , and may contain an oxygen atom or a nitrogen atom between the carbon atoms as long as they are not adjacent to each other). , -R ¹³ -Y ¹ (R ¹³ represents a divalent hydrocarbon group having 0 to 14 carbon atoms, and may contain an oxygen atom or a nitrogen atom between carbon atoms unless they are adjacent to each other). represents at least one an integer of .n is 0 to 10000 .l comprising functional groups ^{Y 1} is representing an integer of .m is 1 to 1000, which represents an integer of 1 to 10000 The compound shown by this can be illustrated.

R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are all non-hydrolyzable groups. Preferred examples include alkyl groups having no functional group Y ¹ such as CH ₃ , C ₂ H ₅ , C ₃ H ₇ ; Y ¹ —CH ₂ —, Y ¹ —CH ₂ CH ₂ —, Y ¹ —CH. Functional group Y ¹ -containing alkyl group such as ₂ CH ₂ CH ₂ —; —CH ₂ —Rf ¹ , —CH ₂ CH ₂ —Rf ¹ (Rf ¹ represents a C 1-18 fluoroalkyl group. Fluorine atom The number of is not particularly limited.) A fluorine-containing alkyl group having no functional group Y ¹ such as: —CH ₂ —Rf ² , —CH ₂ CH ₂ —Rf ² , —CH ₂ CH ₂ CH ₂ —Rf ² (Rf ^2, the number of representative. fluorine atom a fluoroalkyl group having 1 to 18 carbon atoms having a functional group Y ¹ is a fluorine-containing alkyl group, and the like, in particular without limitation.) having the functional group Y ¹ such.

Specific examples of Rf ¹ include the following.

Fluoroalkyl group having no functional group Y ^1:
_{C 4 F 9 C 2 H 4} -, C 8 F 17 C 2 H 4 -, C 9 F 19 C 2 H 4 -, C 4 F 9 SO 2 N (CH 3) C 2 H 4 -, C 4 F ₉ C ₂ H ₄ N (CH ₃ ) C ₃ H ₉ -etc.

Fluoroether group having no functional group Y ^1:
_{CF 3 OCF 2 CF 2 O-} C 2 H 4 -, CF 3 (CF 2 CF 2 O) 2 -C 2 H 4 -, CF 3 O (CF 2 O) 2 (CF 2 CF 2 O) 2 -, _{CF 3 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) 7 -, F- (C 3 F 6 O) 6 - (C 2 F 4 O) 2 - , etc.

Specific examples of Rf ² include the following.

A fluoroalkyl group having a functional group Y ^1:
_{OHC 2 H 4 CF 2 CF 2} CF 2 CF 2 C 2 H 4 -, HOOCCF 2 CF 2 CF 2 CF 2 C 2 H 4 - , etc.

Fluoroether group having a functional group Y ^1:
_{HOCH 2 CF 2 O (CF2CF 2} O) 3 -C 2 H 4 -, HOOCCF 2 O (CF 2 CF 2 O) 3 -, C 2 H 4 - , etc.

From the viewpoint of excellent water and oil repellency, at least one of these is preferably a fluoroalkyl group or a fluoroether group having no functional group Y ^1.

Examples of the functional group Y ¹ include those described above, but they are preferably bonded in the following manner.

(In the formula, R ¹ is the same as above. R ¹⁴ represents an alkylene group having 0 to 8 carbon atoms. R ¹⁵ represents an alkylene group having 0 to 8 carbon atoms. A and b represent positive integers.) .)

Specific examples of the functional group Y ¹ -containing polydialkylsiloxane (B1) are illustrated as follows by commercially available products according to the type of the functional group Y ¹ .

The functional group Y ¹ is —OH:
Silaplane FM-4421, FM-0421, FM-0411, FM-0425, FM-DA11, FM-DA21, etc. (above, manufactured by Chisso Corporation);
KF-6001, KF-6002, X-22-4015, X-22-176DX, etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.)

The functional group Y ¹ is —NH ₂ or —R ¹⁴ —NH—R ¹⁵ —NH ₂ : (wherein R ¹⁴ and R ¹⁵ are the same as above).
Sailor plane FM-3321, FM-3331, FM-3325, etc. (above, manufactured by Chisso Corporation);
KF-860, KF-861, KF-865, KF-8002, X-22-161B, etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
FZ-3501, FZ-3789, FZ-3508, FZ-3705, FZ-4678, FZ-4671, FZ-4658, etc. (above, manufactured by Nihon Unicar Co., Ltd.)

Functional group ^{Y 1} is an epoxy group:
Silaplane FM-0521, FM-5521, FM-0511, FM-0525, etc. (above, manufactured by Chisso Corporation);
KF-101, X-22-163B, X-22-169B etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
L-9300, FZ-3736, FZ-3720, LE-9300, FZ-315 and the like (manufactured by Nihon Unicar Co., Ltd.)

The functional group Y ¹ is —COOH:
X-22-162C, X-22-3701E, etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.);
FZ-3703, etc. (Nippon Unicar Co., Ltd.)

The functional group Y ¹ is —SH:
KF-2001, X-22-167B, etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.)

The functional group Y ¹ is — (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b R ¹ (wherein R ¹ is the same as above):
KF-353, KF-355A, KF-6015, etc. (above, manufactured by Shin-Etsu Chemical Co., Ltd.)

Next, the fluoropolyether (B2) will be described in detail.

The fluoropolyether (B2) has at least one functional group Y selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, a carboxyl group, a thiol group, a nitrile group, an iodine atom, and a hydrolyzable alkylsilicate residue. ² is preferably contained.

The hydrolyzable alkyl silicate residue is preferably the same as that described for the polydialkylsiloxane (B1).

As the functional group ^{Y 2} containing fluoropolyether (B2), the following equation (2):

(In the formula, R ¹⁶ represents H, an alkyl group having 1 to 8 carbon atoms, F, or C _q F _{2q + 1} O— (q represents an integer of 1 to 5.) Y ² is the above. L, m, n, p and r are the same or different and each represents an integer of 0 to 200 and are not all zero.

R ¹⁶ includes H; F; a non-fluorinated alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; a C 1 to 15 carbon atom such as CF ₃ and C ₂ F ₅ Y ² — (CH ₂ ) _s —C _q F _2q O— (q represents any integer of 1 to 5. s represents any integer of 0 to 200. Y ² represents the above. And a perfluoroalkoxy group, and the like, and a perfluoroalkyl group is particularly preferable from the viewpoint of excellent water and oil repellency.

Examples of the functional group Y ² include those described above, but they are preferably bonded in the following manner.

^{(Wherein, R 15} is ^{.R 17} and ^{R 18} are as defined above are the same or different, one of the following as ^{.R 19} represents an alkyl group having 1 to 4 carbon atoms:

).

Specific oligomers of the functional group Y ² -containing fluoropolyether (B2) are exemplified for each type of the functional group Y ² as follows.

The functional group Y ² is —OH:
_{F (C 3 F 6 O)} n CF 2 CF 2 CH 2 OH (n is any integer of _{10~14.), OHCH 2 CF 2} O (CF 2 CF 2 O) n - (CFO) m -CF ₂ CH ₂ OH (average of n is 25, the average of m is 5.), etc.

The functional group Y ² is —NH ₂ or —NH—R ¹⁵ —NH ₂ :
_{F (C 3 F 6 O)} n CF 2 CF 2 CH 2 NH 2 ( average of n is 12.) And the like

Functional group ^{Y 2} is an epoxy group:

(The average of n is 16.) etc.

The functional group Y ² is —COOH:
_{F (C 3 F 6 O)} n CF 2 CF 2 COOH ( average of n is 25.) And the like

Functional group ^{Y 2} is -I (iodine):
_{F (C 3 F 6 O)} n CF 2 CF 2 I ( average of n is 10.) And the like

In addition, those described in US Pat. No. 5,279,820 can also be used.

The functional group X of the fluororesin (A) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a carbonyl group, a nitrile group, and a hydrolyzable alkyl silicate residue. Preferred is a group.

Among these, the point of excellent reactivity with the functional group Y ¹ or Y ² of the antifouling component (B), the point of good reactivity with the curing agent (C) such as an isocyanate compound, and the adhesion are improved. In view of the ability, a hydroxyl group or a hydrolyzable alkyl silicate residue is particularly preferable.

The functional group X-containing fluororesin (A) includes the following forms.
(I) a copolymer of a fluoroolefin and a functional group X-containing non-fluorinated monomer,
(II) a copolymer of a functional group X-containing fluoroolefin and a fluoroolefin having no functional group X;
(III) Functional group X-containing fluororesin blend prepared by blending two or more kinds of resins,
(IV) A composite resin (seed polymer) obtained by seed-polymerizing a fluorine resin particle with a functional group X-containing non-fluorinated monomer.

Examples of fluoroolefins include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), perfluoro (alkyl vinyl ether), trifluoroethylene, vinylidene fluoride (VdF), and vinyl fluoride. Can be mentioned.

Moreover, as a functional group X containing fluoroolefin, the following can be illustrated.

(I) CF ₂ = CF (CF ₂ ) _a Z
(Z represents SO ₃ M or COOM (M represents H, NH ₄ or an alkali metal). A is an integer of 1 to 10.)
Specific _examples, CF ₂ = CFCF ₂ -COOH and the like.

_{(Ii) CF 2 = CF (} CF 2 CF (CF 3)) b -Z
(Z represents SO ₃ M or COOM (M represents H, NH ₄ or an alkali metal). B is an integer of 1 to 5.)
Specific _{examples, CF 2 = CFCF 2 CF (} CF 3) -COOH, CF 2 = CF (CF 2 CF (CF 3)) 2 -COONH 4 , and the like.

_{(Iii) CF 2 = CF-} O- (CFRf 3) c -Z
(Rf ³ represents F or CF _3. Z represents SO ₃ M or COOM (M represents H, NH ₄ or an alkali metal). C is an integer of 1 to 10.)
Specific examples include CF ₂ ═CF—O—CF ₂ CF ₂ CF ₂ COOH.

_{(Iv) CF 2 = CF-} O- (CF 2 CFRf 3 O) d -Z
(Rf ³ represents F or CF _3. Z represents SO ₃ M or COOM (M represents H, NH ₄ or an alkali metal). D is an integer of 1 to 10.)
Specific examples include CF ₂ ═CF—O—CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH, CF ₂ ═CF—O—CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ H, and the like. .

_{(V) CH 2 = CFCF 2} -O- (CF (CF 3) CF 2 O) e -CF (CF 3) -Z
(Z represents SO ₃ M or COOM (M is H, NH ₄ or an alkali metal). E is an integer of 0 to 10.)
Specific examples include the following.

_{(Vi) CF 2 = CFCF 2} -O- (CF (CF 3) CF 2 O) f -CF (CF 3) -Z
(Z is SO ₃ M or COOM (M is H, .f representing the NH ₄ or an alkali metal) is any integer from 1 to 10.)
Specific _{examples, CF 2 = CFCF 2 O-} CF (CF 3) CF 2 O-CF (CF 3) COOH, CF 2 = CFCF 2 O-CF (CF 3) CF 2 O-CF (CF 3) SO ₃ H and the like.

Among the functional group X-containing non-fluorinated monomers, the hydroxyl group-containing non-fluorinated monomers include the following formula (3):

(Wherein, R ²⁰ represents —OR ²¹ or CH ₂ OR ²¹ (R ²¹ represents an alkyl group having a hydroxyl group)), and a hydroxyalkyl vinyl ether or hydroxyallyl ether represented by

Examples of R ²¹ include those in which 1 to 3 hydroxyl groups are bonded to a linear or branched alkyl group having 1 to 8 carbon atoms, and preferably one hydroxyl group is bonded.

Specific examples of R ²¹ include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl. Examples include vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether. Other examples include allyl alcohol.

Non-fluorinated monomers containing hydrolyzable alkyl silicate residues include vinyl alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane; trimethoxysilylethyl vinyl ether; Examples include triethoxysilylethyl vinyl ether; triethoxysilylpropyl vinyl ether; triisopropenyloxysilylethyl vinyl ether; γ- (meth) acryloyloxypropyltrimethoxysilane and the like.

As carboxyl group-containing non-fluorinated monomers, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, itaconic anhydride, succinic anhydride And carboxyl group-containing monomers such as maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, and 3-allyloxypropionic acid.

Other functional group X-containing non-fluorinated monomers include epoxy group-containing monomers such as glycidyl (meth) acrylate, epoxy vinyl, and epoxy vinyl ether; diacetone acrylamide, (meth) acrylamide, N-methylol (meta Examples thereof include amino group-containing monomers such as acrylamide; nitrile group-containing monomers such as (meth) acrylonitrile; carbonyl group-containing monomers such as acrolein, vinyl ethyl ketone and diacetone acrylamide.

Moreover, you may use the monomer which does not have said functional group X as a comonomer. For example, α-olefins such as ethylene, propylene and isobutylene; vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether and polyoxyethylene vinyl ether; polyoxyethylene allyl ether; Alkenyls such as ethyl allyl ether and allyl ether; vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, saturated vinyl carboxylate (for example, Veova 9 and Veova 10 manufactured by Shell Chemical Co., Ltd.) ; Unsaturated carboxylic acid diesters such as dimethyl maleate; (meth) acrylic acid esters such as methyl methacrylate and butyl acrylate; vinyl styrene such as styrene and vinyltoluene Aromatic compounds or the like can be used.

Among the copolymers of the form (I), the hydroxyl group-containing copolymer includes the fluoroolefin, a hydroxyl group-containing monomer, and a monomer copolymerizable with these monomers if necessary. The copolymer of these is mentioned. A typical example of the hydroxyl group-containing monomer is hydroxybutyl vinyl ether, and a typical example of the carboxyl group-containing monomer is maleic acid. Examples of other comonomers include alkyl vinyl esters, alkyl vinyl ethers, olefins such as ethylene, propylene, and isobutene, (meth) acrylates, and styrene.

Specifically, as described in JP-B-60-21686, JP-A-3-121107, JP-A-4-279612, JP-A-4-28707, JP-A-2-232221, and the like. Things. The number average molecular weight (by GPC) of the copolymer is preferably 1000 to 100,000, more preferably 1500 to 30000. If the number average molecular weight is less than 1000, curability or weather resistance tends to be insufficient, and if it exceeds 100,000, there is a tendency for problems to occur in workability or film formability.

More specifically, TFE / alkyl vinyl ether / HBVE copolymer, CTFE / alkyl vinyl ether / HBVE copolymer, TFE / alkyl vinyl ether / maleic acid copolymer, CTFE / alkyl vinyl ether / maleic acid copolymer Examples include coalescence.

As a hydroxyl value of the said copolymer, 10-300 (mgKOH / g) is preferable, 10-200 (mgKOH / g) is more preferable, 10-150 (mgKOH / g) is still more preferable. When the hydroxyl group is reduced, curing tends to be poor, and when it exceeds 200 (mgKOH / g), the flexibility of the film tends to be problematic.

As an acid value of the said copolymer, 0.5-100 (mgKOH / g) is preferable, and 0.5-50 (mgKOH / g) is more preferable. When the acid value decreases, the curing tends to be poor, and when the acid value exceeds 100 (mgKOH / g), the flexibility of the film tends to be problematic.

Commercially available products of the above-mentioned copolymers include Zaffle manufactured by Daikin Industries, Ltd., Lumiflon manufactured by Asahi Glass Co., Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., Fluonate manufactured by Dainippon Ink & Chemicals, Inc., Toa Gosei Examples include ZAFLON manufactured by Co., Ltd.

Among the functional group-containing fluorine-containing copolymer (I), examples of the fluoroolefin resin having a hydrolyzable alkyl silicate residue as a functional group include those described in JP-A-4-4246. Can be mentioned. The number average molecular weight (by GPC) of the copolymer is preferably 1000 to 100,000, more preferably 1500 to 30000. If the number average molecular weight is less than 1000, curability or weather resistance tends to be insufficient, and if it exceeds 100,000, there is a tendency for problems in workability or film formability.

More specifically, a copolymer containing TFE / vinylmethoxysilane, a copolymer containing TFE / trimethoxysilylethyl vinyl ether, and the like can be given.

As content of the hydrolysable alkyl silicate residue of the said copolymer, 1-50 mol% is preferable, More preferably, it is 5-40 mol%. If the hydrolyzable alkyl silicate residue is reduced, the curing tends to be poor, and if it is too much, the flexibility of the film tends to be problematic.

Other examples of the copolymer (I) include CTFE / ethyl vinyl ether / 2-hydroxybutyl vinyl ether copolymer, TFE / cyclohexyl vinyl ether / veova 10 / crotonic acid copolymer, and the like.

Examples of the copolymer (II) include TFE / HFP / functional group X-containing fluorine-containing monomer-based copolymer represented by the above formulas (i) to (vi).

A functional group X-containing fluorine-containing monomer-based copolymer having a relatively high fluorine content is preferable from the viewpoint of good antifouling properties, weather resistance, etc. and a low refractive index. The fluorine content is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. The upper limit is the fluorine content of the perfluororesin in which all the hydrogen atoms of each resin are replaced with fluorine atoms.

In addition, the functional group X-containing fluorine-containing monomer-based copolymer is preferable in that a lower refractive index is excellent in transparency and sharpness is improved. Preferably, the refractive index is 1.6 or less, more preferably 1.5 or less. Preferably, the refractive index is 1.3 or more.

As the blend (III), a blend of the copolymers (I) or (II), a blend of the copolymer (I) or (II) and the functional group X-containing non-fluorinated resin, a copolymer Examples thereof include a blend of (I) or (II) with a non-fluorinated resin not containing functional group X, a blend of a functional group X-containing non-fluorinated resin and a fluorine resin not containing functional group X, and the like.

Examples of the functional group X-containing non-fluorinated resin include (co) polymers of the above functional group X-containing monomers, and specific examples include acrylic polyols and urethane polyols. Examples of non-fluorinated resins that do not contain the functional group X include acrylic resins and polyesters. Examples of fluororesins that do not contain functional group X include VdF homopolymers, VdF / TFE copolymers, VdF / HFP copolymers, VdF / CTFE copolymers, VdF / TFE / CTFE copolymers. VdF polymers such as polymers, VdF / TFE / HFP copolymers; TFE / HFP copolymers; non-fluorinated monomers having no fluoroolefin and functional group X (for example, vinyl ethers, vinyl esters) , Α-olefins, or vinyl aromatic compounds).

The blend ratio may be appropriately selected depending on the content of the functional group X, the fluorine content, etc. The amount of the functional group X that can sufficiently react with the antifouling component (B) and further the curing agent (C) It is desirable to blend so that the antifouling property is excellent.

As the composite resin (seed polymer) (IV), a non-fluorinated monomer containing the functional group X is seed-polymerized in an aqueous dispersion of fluororesin particles with or without the functional group X. What was manufactured in this way can be illustrated preferably. Specifically, a composite resin obtained by seed polymerization of acrylic acid, methacrylic acid, (meth) acrylic acid ester, a functional group X-containing vinyl compound or the like in an aqueous dispersion of VdF copolymer particles is preferable. .

The functional group X-containing fluororesin can be used in the form of an organic solvent composition or an aqueous dispersion composition, but the composite resin is particularly useful when used as an aqueous dispersion composition. Desired conditions when used as an organic solvent composition and when used as an aqueous dispersion composition will be described later.

As described above, the antifouling composition of the present invention essentially contains the fluororesin (A) containing the functional group X, and the antifouling component (B) and the curing agent are combined with the functional group X. (C) is preferably blended as appropriate.

The blending amount of the antifouling component (B) with respect to 100 parts by mass of the fluororesin (A) is preferably 0.01 to 50 parts by mass. A more preferred lower limit is 0.1 parts by mass, and a more preferred upper limit is 20 parts by mass. If the antifouling component (B) is too much, the film formability and weather resistance tend to be lowered, and if it is too little, the water and oil repellency tends to be lowered.

And the functional group Y ¹ or Y ² functional groups X and antifouling component of the fluororesin (A) (B) are hydroxyl groups, a hydroxyl group and an amino group, among carboxyl group, a carboxyl group and an amino group, a carboxyl group and an epoxy group In the case of amino groups or epoxy groups, it is preferable to further add a curing agent (C). In the case of a combination of a hydroxyl group and a hydrolyzable alkyl silicate residue, a curing agent (C) may be used.

The kind of the curing agent (C) is appropriately selected depending on the combination of the functional group X and the functional group Y ¹ or Y ² .

Specific examples of preferable curing agents (C) include amino compounds, epoxy compounds, organic acids, hydrazide compounds, aziridine compounds, carbodiimide compounds, Si (OR ⁴ ) ₄ (R ⁴ is a non-fluorinated alkyl group having 1 to 10 carbon atoms). A compound containing R ⁵ Si (OR ⁶ ) ₃ (R ⁵ and R ⁶ are the same or different and each represents a non-fluorinated alkyl group having 1 to 10 carbon atoms), Examples thereof include at least one selected from the group consisting of a single condensation oligomer formed from these compounds and a cocondensation co-oligomer formed from these compounds.

Although the compounding quantity of a hardening | curing agent (C) is suitably adjusted with the kind of hardening | curing agent, Preferably, it is 0-200 mass parts with respect to a total of 100 mass parts of a fluororesin (A) and an antifouling component (B). is there. A more preferred upper limit is 100 parts by mass, and a still more preferred upper limit is 80 parts by mass. A more preferred lower limit is 5 parts by mass, and a still more preferred lower limit is 10 parts by mass.

Hereinafter, examples of a combination of functional groups of the fluororesin (A) and the antifouling component (B) and a curing agent (C) suitable for the combination will be given.

(1) When the functional group X of the fluororesin (A) is a hydroxyl group and the functional group Y ¹ or Y ^{2 of} the antifouling component (B) is a hydroxyl group or an amino group, the curing agent (C) is Isocyanate compounds are preferred.

The isocyanate compound includes a blocked isocyanate compound. Specific examples of the isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate. N-pentane-1,4-diisocyanate, trimers thereof, adducts thereof, burettes thereof, polymers having two or more isocyanate groups, lysine triisocyanate (specifically, 2-isocyanatoethyl 2,6-diisocyanatohexanoate, etc.), blocked isocyanates and the like.

In addition, an isocyanate compound having a hydrolyzable alkyl silicate residue can also be preferably used.

As the hydrolyzable alkyl silicate residue, those described for the polydialkylsiloxane (B1) or the fluoropolyether (B2) are preferably used.

Specific examples of the isocyanate compound having a hydrolyzable alkyl silicate residue include OCNC ₃ H ₆ Si (OCH ₃ ) ₃ , OCNC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ , and OCNC ₃ H ₆ Si (OCOCH ₃ ). ₃ , OCNC ₃ H ₆ Si (CH ₃ ) (OCH ₃ ) _{3 and the} like.

The mixing ratio of the isocyanate compound and the fluororesin (A) is preferably NCO / OH (molar ratio) of 0.5 to 5.0, more preferably 0.8 to 1.5. Moreover, when an isocyanate compound is a moisture hardening type, 1.1-1.5 are preferable.

As the curing agent (C), instead of or in addition to the isocyanate compound, Si (OR ⁴ ) ₄ (R ⁴ represents a non-fluorinated alkyl group having 1 to 10 carbon atoms), R ⁵ Si (OR ⁶ ) ₃ (R ⁵ and R ⁶ are the same or different and represent a non-fluorinated alkyl group having 1 to 10 carbon atoms), a single condensed oligomer thereof, and a co-condensed co-oligomer thereof. At least one kind can also be used.

As these tetrafunctional or trifunctional non-fluorinated alkyl silicates, for example, those described in US Pat. No. 5,635,572 and the like can be used.

Specific examples include tetraalkoxysilane, tetraalkoxysilane condensate, alkyltrialkoxysilane, alkyltrialkoxysilane condensate, polysilsesquioxane, colloidal silica, and the like.

Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, condensates thereof, and the like. Commercially available products include MS51, MS56, MS57, etc. manufactured by Mitsubishi Chemical Corporation, manufactured by Colcoat. Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48, etc. can be used.

Examples of the polysilsesquioxane include polyphenylsilsesquioxane, polymethylsilsesquioxane, polyhydrogensilsesquioxane, and the like.

As the colloidal silica, Snowtex manufactured by Nissan Chemical Co., Ltd. can be used.

Among these, a tetraalkoxysilane condensate is preferable because it can form a strong coating film having a high crosslinking density.

Although the compounding quantity of such a silicate type | system | group hardening | curing agent is suitably selected according to the kind of hardening | curing agent, it is 0-100 mass parts with respect to a total of 100 mass parts of a fluororesin (A) and an antifouling component (B). It is preferable. A more preferable upper limit is 50 parts by mass, and a more preferable lower limit is 10 parts by mass.

The hydroxyl group-containing fluororesin used in this combination preferably has a hydroxyl value of 10 mgKOH / g or more, preferably 50 mgKOH / g or more from the viewpoint of increasing the crosslinking density and improving the film strength. The upper limit of the hydroxyl value is preferably 300 mgKOH / g, more preferably 200 mgKOH / g. If it is too large, there may be a problem in the flexibility of the film.

Further, the fluorine content of the hydroxyl group-containing fluororesin is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more to improve antifouling properties and weather resistance. From the viewpoint of lowering the refractive index. The upper limit is the fluorine content of the perfluororesin in which all hydrogen atoms are replaced with fluorine atoms.

The functional group Y ¹ or Y ² of the antifouling component (B) is particularly preferably an amino group from the viewpoint of good reactivity with the isocyanate compound used as the curing agent (C).

In this case, the amino equivalent of the antifouling component (B) is preferably 1000 or more.

The amino equivalent is an index of the number of amino groups per number average molecular weight 10,000 and is a value represented by “(number average molecular weight 10,000) / (number of amino groups per number average molecular weight 10,000)”. Therefore, the larger the amino equivalent, the smaller the number of amino groups in the compound having the same molecular weight.

A preferred amino equivalent is 1500 or more, more preferably 3000 or more, and still more preferably 10,000 or more. The upper limit is 50,000. If the amino equivalent is too small (the number of amino groups is too large), the reaction with the isocyanate compound precedes the reaction with the hydroxyl group of the hydroxyl group-containing fluororesin, and the isocyanate compound and the antifouling component (B) are combined. The body may form and become particles, which may impair the film appearance.

However, if such large particles are removed by filtration with a mesh having a pore size of 50 μm, for example, the appearance of the film is not impaired.

(2) When the functional group X of the fluororesin (A) is a carboxyl group and the functional group Y ¹ or Y ^{2 of} the antifouling component (B) is a carboxyl group, an amino group or an epoxy group, a curing agent (C) is preferably an amino compound, an epoxy compound, an aziridine compound or a carbodiimide compound.

Examples of the amino compound curing agent include melamine resin, urea resin, guanamine resin, amine adduct, and polyamide.

As commercial products, Cymel manufactured by Nippon Cytec Co., Ltd., a regimen manufactured by Solusia, Ancamine and Epilink manufactured by Air Products, Versamine and Versamide manufactured by Henkel, Tomide and Fujicure manufactured by Fuji Kasei Kogyo Co., Ltd. Examples include Versamide manufactured by Dai-ichi General Co., Ltd., EpiCure manufactured by Japan Epoxy Resin Co., Ltd., Sanmide manufactured by Sanwa Chemical Co., Ltd., and Epomet manufactured by Ajinomoto Co., Inc.

Examples of the epoxy compound curing agent include an epoxy resin, an epoxy-modified silane coupling agent, etc., and commercially available products include Epicoat and Epirec manufactured by Japan Epoxy Resin Co., Ltd., Cardlight manufactured by Cardlight, Nippon Unicar Co., Ltd. ) Coated Jill 1770 and A-187.

Examples of the aziridine compound-based curing agent include XAMA2 and XAMA7 manufactured by BF-Goodrich.

Examples of the carbodiimide compound-based curing agent include Nisshinbo Carbodilite, Union Carbide UCARLNK Crosslinker XL-29SE, and the like.

(3) When the functional group X of the fluororesin (A) is an amino group and the functional group Y ¹ or Y ^{2 of} the antifouling component (B) is an amino group or a carboxyl group, the curing agent (C) As such, an epoxy compound or an organic acid is preferable.

As an epoxy compound type hardening | curing agent, what was illustrated by said (2) can be used.

Examples of the organic acid curing agent include polyvalent carboxylic acids such as phthalic anhydride, adipic acid, and succinic acid, and polyacrylic acid.

(4) the functional group X having the fluororesin (A) is is an epoxy group, if the functional group Y ¹ or Y ² have antifouling component (B) is an amino group or an epoxy group, the curing agent (C) As such, an organic acid or an amino compound is preferable.

As the organic acid curing agent, those exemplified in the above (3) can be used.

As the amino compound-based curing agent, those exemplified in the above (2) can be used.

(5) The fluororesin (A) is a functional group X having is carbonyl group or a carboxyl group, if antifouling component (B) is a functional group Y ¹ or Y ² has is an amino group or a carboxyl group, curing agent (C) is preferably an epoxy compound or a hydrazide compound.

Examples of the hydrazide compound-based curing agent include malonic acid dihydrazide, glutaric acid dihydrazide, hydrazine, maleic acid dihydrazide, and adipic acid dihydrazide.

Among these, a particularly preferable combination is a functional group Y ¹ or Y of the antifouling component (B) in which the functional group X of the fluororesin (A) is a hydroxyl group in consideration of reactivity and ease of synthesis. ² is an amino group, and the curing agent (C) is an isocyanate compound, particularly an isocyanate curing agent having a hydrolyzable alkyl silicate residue.

In the antifouling composition of the present invention, a curing catalyst (D) may be used instead of or in addition to the curing agent (C).

In particular, when the fluororesin (A) has a hydrolyzable alkyl silicate group and the antifouling component (B) has a hydroxyl group or a hydrolyzable alkyl silicate residue, or the fluororesin (A) has a hydroxyl group. In the case where the antifouling component (B) has a hydrolyzable alkyl silicate residue, the functional group X of the fluororesin (A) and the antifouling component (B) are not necessary even if the curing agent (C) is not particularly added. The functional group Y ¹ or Y ² sufficiently causes a curing reaction.

Examples of the curing catalyst (D) include an organic tin compound, an organic acidic phosphate ester, an organic titanate compound, a reaction product of an acidic phosphate ester and an amine, a saturated or unsaturated polycarboxylic acid or an acid anhydride thereof, and an organic sulfone. Examples thereof include acids, amine compounds, aluminum chelate compounds, titanium chelate compounds, and zirconium chelate compounds.

Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate and the like.

Specific examples of the organic acid phosphate ester include the following.

Examples of the organic titanate compound include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.

Specific examples of the amine compound include butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Amines such as triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) Compounds, salts of such carboxylic acids, low molecular weight polyamide resins obtained from excess polyamines and polybasic acids, reaction products of excess polyamines and epoxy compounds, etc.

Specific examples of the chelate compound include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), zirconium tetrakis (acetylacetonate), diisopropoxy bis (ethylacetoacetate) titanate and the like.

1 type may be used for a curing catalyst (D) and it may use 2 or more types together. Preferable curing catalysts (D) include organotin compounds and aluminum chelate compounds. The compounding quantity of a curing catalyst (D) is 0-10 mass parts with respect to a total of 100 mass parts of a fluororesin (A), an antifouling component (B), and a hardening | curing agent (C), Preferably it is 0.001-5 mass. Part.

The antifouling composition of the present invention contains an organic solvent and is used as an organic solvent composition.

Organic solvents include xylene, toluene, Solvesso 100, Solvesso 150, hexane and other hydrocarbon solvents; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether , Ester solvents such as acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol monobutyl ether, acetic acid ethylene glycol, acetic acid diethylene glycol, etc .; dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl ether, ethylene glycol dimethyl ether Ether solvents such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran; methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. Ketone solvents; Amide solvents such as N, N-dimethylacetamide, N-methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylformamide; Sulfonic acid esters such as dimethylsulfoxide Solvent: methanol, ethanol, isopropyl Nord, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (polymerization degree of _{3~100), CF 3 CH 2 OH} , F (CF 2) 2 CH 2 OH, (CF 3) 2 CHOH, F (CF 2) 3 CH 2 Alcohol solvents such as OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ OH, etc. Among them, alcohol solvents such as lower alcohols and lower fluorine alcohols are preferable from the viewpoints of compatibility, film appearance, and storage stability.

As for the blending ratio of the fluororesin (A) and the alcohol solvent, the alcohol solvent is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the fluororesin (A), and the point of curability and film appearance. 1 to 25 parts by mass is more preferable.

In addition, when the curing agent is highly reactive with an alcohol such as a room-temperature curable isocyanate, the alcohol is more preferably 1 to 15 parts by mass, and the type of alcohol is preferably a secondary or tertiary alcohol. .

The antifouling composition of the present invention is used as an aqueous dispersion composition by dispersing each component in an aqueous medium.

When used as an aqueous dispersion type composition, the solid content concentration is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, from the viewpoint of excellent stability when forming a film. The average particle size is preferably 50 to 300 nm, more preferably 100 to 250 nm, from the viewpoint of excellent stability of the aqueous dispersion. The pH is preferably in the range of 5-10.

When preparing an aqueous dispersion composition, it is preferable to use a water-soluble or water-dispersible curing agent (C) and curing catalyst (D).

Also in the aqueous dispersion type composition, the above-mentioned various additives can be blended. In addition, in order to improve film forming property, it is preferable to mix | blend a film forming adjuvant. Examples of the film-forming aid include diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethyl adipate, dibutyl adipate, and the like. Commercially available products include CS-12 manufactured by Chisso Corporation, DBE and DBE manufactured by DuPont. -IB etc. can be used.

Further, in order to provide dispersion stability of the aqueous dispersion, it is preferable that a surfactant is present. Surfactants include fluorine-based surfactants such as ammonium perfluorooctanoate and ammonium perfluorononanoate; nonionic non-fluorine-based surfactants such as polyoxyethylene alkyl ether and sorbitan alkyl ester; sodium alkylsulfonate And anionic non-fluorine surfactants such as sodium dialkyl ester succinate; amphoteric surfactants such as lauryl betaine and sodium polyoxyethylene nonyl ether sulfate.

The antifouling composition of the present invention includes pigments, pigment dispersants, thickeners, leveling agents, antifoaming agents, film-forming aids, UV absorbers, HALS, matting agents, fillers, colloidal silica, and antifungal agents. , Silane coupling agents, anti-skinning agents, antioxidants, flame retardants, anti-sagging agents, antistatic agents, rust inhibitors, water-soluble resins (polyvinyl alcohol, polyethylene oxide, etc.), antiseptics, antifreeze agents, etc. Ordinary additives can also be blended.

Examples of the pigment include titanium oxide, iron oxide, aluminum metallic pigment, carbon black, calcined pigment, phthalocyanine pigment, organic pigment, extender pigment and the like.

As the ultraviolet absorber, a benzophenone-based or benzotriazole-based compound is suitable.

More preferably, if it is a benzophenone series, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, or 2,2 ′, 4,4′-tetra Hydroxybenzophenone.

If it is a benzotriazole type, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -5,6-dichlorobenzo is more preferable. Triazole), 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chloro-benzotriazole 2- (2′-hydroxy-5′-phenylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tertbutylphenyl) -5-chlorobenzotriazole, 2- (2′- Hydroxy-3 ′, 5′-ditertbutylphenyl) benzotriazole, or 2- (2′-hydroxy-5′-tert) Kuchirufeniru) benzotriazole.

A particularly suitable ultraviolet absorber is represented by the following formula (4):

(Wherein R ²² and R ²³ are the same or different and each represents a hydrogen atom, a lower alkyl group (preferably a branched lower alkyl group), or an aryl group (preferably a phenyl group). A hydrogen atom or a halogen atom (preferably a chlorine atom).

Examples of the HALS include Tinuvin-400, 479, 770, 292, 622, 123, and 440 manufactured by BASF Corporation.

Examples of the matting agent include silicia 350 and 380 manufactured by Fuji Silysia Chemical Co., Ltd., silo hovic 200, celitet # 3620, # 9615A, # 9612A, # 3715, and # 3910 manufactured by Hoechst Industry Co., Ltd., Hoechst wax, etc. PE520, white carbon, etc. are mentioned.

Examples of the silane coupling agent include methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropyl isocyanate, 3-triethoxysilylpropyl isocyanate, methyltris (Ethylmethylketoxime) silane and the like can be mentioned, and those containing at least one of an alkylketoxime group and an isocyanate group are preferable.

The antifouling composition of the present invention may be applied directly to an exhaust duct, a grease filter or a range hood, or may be used as a material for an antifouling film.

Hereinafter, usage examples of the antifouling composition of the present invention will be described in detail. First, an example in the case of using as an antifouling film material will be described.

As an aspect of the antifouling film to be produced, (a) a single layer film made of a coating film formed from the above antifouling composition, and (b) a coating film formed from the above antifouling composition; And a laminated film including a layer formed from a fluorinated polymer.

The coating film may be a film obtained by applying an antifouling composition to a release substrate, drying or curing the film, and then peeling it off from the release substrate. As an aspect of the laminated film (b), (b1) a laminated film in which the coating film and the layer formed from the non-fluorinated polymer are directly overlapped, and (b2) the coating film and the non-fluorinated polymer. A laminated film in which the formed layer is overlapped via an adhesive layer is exemplified. For each of these films, an adhesive layer may be further provided in advance on the surface that is attached to the exhaust duct, grease filter, or range hood.

When producing the monolayer film of the above (a), a casting method, an air spray method, a dipping method, a flow coating method, a spin coating method, a roll coating method and the like are used.

For example, in the air spray method, the blended antifouling composition is applied onto a release substrate (film, sheet, plate, etc.) by air spray, left at room temperature for 30 minutes, and then baked at 100 ° C. for about 30 minutes. And then curing, and then peeling off from the release substrate is simple. When the antifouling composition is allowed to stand and dry, the antifouling component (B) gathers at a high concentration near the free surface of the film and is cured in that state, so that the antifouling component (B) is unevenly distributed near one surface. An antifouling film can be formed.

In addition, according to the flow coat method, the blended antifouling composition is applied on a release substrate with a flow coater, left at room temperature for 10 minutes, and then baked and cured at 100 ° C. for about 30 minutes. By the method of peeling from the release substrate, an antifouling film in which the antifouling component (B) is unevenly distributed in the vicinity of one surface can be formed.

The method of curing the antifouling composition applied on the mold release substrate is not particularly limited, and treatments such as heating, curing, and active energy ray irradiation are performed according to the types of components contained in the antifouling composition. It is preferable to select appropriately.

As release substrate, general-purpose resins such as polypropylene (PP), melamine resin, and PET; fluororesin films such as PTFE, FEP, PFA, VdF-TFE copolymer, TFE-HFP-ethylene copolymer, etc. Metals such as aluminum, iron and stainless steel; inorganic plates such as glass and tiles; Further, even in the case of a material having insufficient releasability, the cured antifouling film can be easily peeled off by previously applying a liquid release agent on the release substrate. Examples of such a liquid mold release agent include silicone oil, fluorine oil, fluorine surfactant, and fluorine phosphate ester. These release agents can be easily washed away after peeling.

In the case where the adhesive layer is formed in advance on the single-layer film of the above (a) thus produced, the adhesive layer was laminated on the surface opposite to the release substrate. Then, it can be set as the laminated | multilayer film containing the coating film (film) formed from the antifouling composition, and an adhesive bond layer by peeling a base material for mold release.

On the other hand, in the case of the laminated film (b), for example, a coating film (film) formed from the antifouling composition by applying and curing the antifouling composition of the present invention on the non-fluorinated polymer layer. And a laminated film comprising a layer formed from a non-fluorinated polymer can be produced. The laminated film (b) is prepared by, for example, producing the single-layer film (a) above, and then directly or adhesively bonding the single-layer film (a) to the non-fluorinated polymer layer. It can also be produced by superimposing them.

Examples of the method for applying the antifouling composition on the non-fluorinated polymer layer include a casting method, an air spray method, a dipping method, a flow coating method, a spin coating method, and a roll coating method.

When the antifouling composition is applied onto the non-fluorinated polymer layer and heated to dry to form a coating film, the temperature depends on the type of curing agent, the coating amount, the type of solvent used, etc. It is preferable to hold at 25 to 100 ° C. for 5 to 72 hours after heat curing at −150 ° C. for 5 to 10 minutes. Moreover, it is more preferable to hold | maintain at 40-50 degreeC for 40 to 50 hours after hardening.

The method of curing the antifouling composition applied on the non-fluorinated polymer layer is not particularly limited, and treatments such as heating, curing, and active energy ray irradiation are performed depending on the types of components contained in the antifouling composition. It is preferable to select appropriately.

The non-fluorinated polymer layer can be formed using, for example, a film made of a commercially available non-fluorinated polymer. The non-fluorinated polymer is preferably at least one polymer selected from the group consisting of polyolefin, polyester, polyamide, polyimide, cellulose, acrylic resin, polyethersulfone, polylactic acid, and polyvinyl alcohol.

Among these, polyester is particularly preferable in terms of excellent heat resistance, rigidity, and adhesion to a fluorinated resin.

Polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), parahydroxybenzoic acid / ethylene terephthalate copolymer. , Hydroxynaphthoic acid / parahydroxybenzoic acid copolymer, biphenol / parahydroxybenzoic acid / phthalic acid copolymer, and the like.

In particular, polyethylene terephthalate (PET) is preferable in terms of ease of handling as a substrate and excellent hardness (strain strength).

Also for the laminated film (b), an adhesive layer may be formed in advance on the surface to be attached to the exhaust duct, grease filter or range hood. In this case, an adhesive layer needs to be provided on the non-fluorinated polymer layer, and as a result, an adhesive layer, a non-fluorinated polymer layer, and a coating film (film) formed from the antifouling composition. It becomes the laminated | multilayer film which are laminated | stacked in this order. Further, when the non-fluorinated polymer layer and the coating film (film) formed from the antifouling composition are overlapped via the adhesive layer, the first adhesive layer and the non-fluorinated polymer layer And the 2nd adhesive bond layer and the coating film (film) formed from the antifouling composition serve as a laminated film which is laminated in this order.

You may form or affix a peeling film or paper with respect to the said adhesive bond layer as needed.

The thickness of the antifouling film of the present invention is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more in both cases of a single layer film and a laminated film. Moreover, 1000 micrometers or less are preferable, 500 micrometers or less are more preferable, and 200 micrometers or less are still more preferable.

The antifouling film of the present invention can be used by directly sticking to various substrates, but it is used for undercoat paint such as wash primer, rust preventive paint, epoxy resin paint, acrylic resin paint, polyester resin paint, urethane paint, etc. You may paste it on top.

Since the exhaust duct, the grease filter, and the range hood are generally made of a metal base material, the antifouling film preferably has characteristics suitable for application to a metal base material.

Examples of the metal-based substrate include a zinc iron plate, a vinyl chloride lining steel plate, a glass wool plate, a hard vinyl chloride plate, a steel plate, and a stainless steel plate.

When a certain adhesive strength to the base material is required, the antifouling film may be attached to the base material through an adhesive as necessary, and the adhesive layer is previously used as described above. A laminated film formed with may be used.

The thickness of the adhesive layer is preferably 1 μm or more, more preferably 3 μm or more. Moreover, it is preferable that it is 500 micrometers or less, More preferably, it is 100 micrometers or less.

The adhesive to be used is not particularly limited as long as the antifouling film and the substrate are not deteriorated, and may be appropriately selected according to the material of the antifouling film, the type of the substrate, the required adhesive strength, and the like.

Specifically, acrylic, vinyl acetate, EVA, epoxy, urethane, cyanoacrylate, urea resin, melamine resin, phenol, synthetic rubber, polyvinyl chloride, silicone, isocyanate And chloroprene, nitrile rubber, and SBR adhesives.

The adhesive can be applied as a solvent type, an emulsion type, or a solid (for example, hot melt type). When used as an adhesive layer of a laminated film, the adhesive layer may be formed by applying or extruding an adhesive to the surface of the antifouling film substrate and drying it.

The antifouling film of the present invention is particularly excellent in antifouling properties against dirt containing an oil and fat component. Therefore, it prevents the components contained in the smoke generated in the kitchen etc. from adhering to the grease filter, the range hood and the exhaust duct, and it is excellent cleaning when removing the adhered dirt. Demonstrate sex.

Further, in the case of an antifouling film, unlike the case of directly applying the antifouling composition, it can be reattached after use for a certain period. Therefore, the continuous antifouling function of the exhaust duct, the grease filter and the range hood is fulfilled by replacing the antifouling film after a certain period. Further, the antifouling film of the present invention does not require frequent replacement.

Then, the example in the case of apply | coating the antifouling composition of this invention directly to an exhaust duct, a grease filter, or a range hood is demonstrated.

In this case, the antifouling composition of the present invention may be applied as it is to the surface of the exhaust duct, grease filter or range hood as it is prepared as an organic solvent type composition or an aqueous dispersion type composition. A manufacturing process such as manufacturing is not required.

As described above, since the exhaust duct, the grease filter, or the range hood is generally made of a metal base material, the antifouling film has characteristics suitable for application to a metal base material. It is preferable.

A method for applying and curing the antifouling composition of the present invention to an exhaust duct, a grease filter and a range hood is not particularly limited, and a known method may be used, for example, a spray coating method (for example, an air spray method). Dip coating method, roll coating method, curtain coating method, die coating method, gravure coating method and the like.

The antifouling composition of the present invention is particularly excellent in antifouling properties against dirt containing an oil and fat component. Therefore, it prevents the components contained in the smoke generated in the kitchen etc. from adhering to the grease filter, the range hood and the exhaust duct, and it is excellent cleaning when removing the adhered dirt. Demonstrate sex.

Specific examples of such dirt removal work are not particularly limited, a method of spraying a cleaning agent, a method of scraping with dry ice, a method of scraping with a brush with wire, a method of cleaning by inserting a steam nozzle, a machine Cleaning method, dust collector cleaning ozone cleaning, high-pressure air cleaning and the like.

Specifically, the antifouling composition and antifouling film of the present invention are used as follows for an exhaust duct, a grease filter and a range hood.

FIG. 1 is a schematic cross-sectional view illustrating an example of an exhaust duct, a grease filter, and a range hood provided in a kitchen. FIG. 2 is a schematic perspective view of the exhaust duct, grease filter, and range hood shown in FIG.

As shown in FIGS. 1 and 2, the exhaust duct 20 is a large pipe that has an intake port 21 and an exhaust port 23 and exhausts smoke generated indoors through the main pipe portion 22 to the outside. The grease filter 30 has a large number of fine slits and is attached to the exhaust duct 20 in front of the air inlet 21 to remove components such as oil and fat contained in smoke generated in a kitchen or the like. The range hood 40 is disposed directly above the gas stove 11 and surrounding the grease filter 30 so that smoke is easily sucked into the air inlet 21 of the exhaust duct 20.

As shown in FIGS. 1 and 2, the smoke 12 generated by using the gas stove 11 or the like enters the pipe of the exhaust duct 20 through the grease filter 30 and is exhausted to the outside through the exhaust port 23 of the exhaust duct 20. In this process, dirt components such as oil and fat contained in the flue gas adhere to the front and back surfaces of the grease filter 30 and the inner surface of the exhaust duct 20.

In order to easily remove the dirt component, the antifouling composition is applied to the inner surface of the exhaust duct 20 or the antifouling film is attached. In addition, the antifouling composition is applied or the antifouling film is attached to the front surface or back surface (preferably both surfaces) of the grease filter 30. Further, the antifouling composition is applied to the inner surface of the range hood 40 or the antifouling film is attached.

The application of the antifouling composition and the application of the antifouling film are particularly applied to portions where dirt adheres or passes, such as the inner surface of an exhaust duct, the surface of a grease filter, the inner surface of a range hood, etc. Preferably applied.

As described above, the exhaust duct, the grease filter and the range hood of the present invention are coated with the antifouling composition or attached with the antifouling film, so that dirt such as oil and fat generated in the kitchen is contaminated. It is difficult to adhere, and the attached dirt can be easily wiped off.

Below, the example which manufactured the antifouling composition of this invention is demonstrated.

Adjustment example 1
To 100 parts of Zeffle GK-570 (manufactured by Daikin Industries, Ltd .; hydroxyl group-containing tetrafluoroethylene copolymer, hydroxyl value 60 mgKOH / g, acid value 4 mgKOH / g, butyl acetate solution, solid content 65%; fluororesin (A)) , 13 parts of Sumijour N-3300 (Sumika Bayer's isocyanate-based curing agent, curing agent (C)) as a curing agent, amino group-containing silicone oil SF8417 (amino-modified silicone oil manufactured by Toray Dow Corning, 0.2 parts of antifouling component (B)) and 190 parts of butyl acetate were added and stirred well to obtain an antifouling composition.

Adjustment example 2
Add 100 parts of Zeffle GK-570 (manufactured by Daikin Industries, Ltd., the same), 13 parts of Sumidur N-3300 (manufactured by Sumika Bayer, the same as the above) as a curing agent and 190 parts of butyl acetate, and stir well to prevent A soil composition was obtained.

Below, the example which manufactured the antifouling film of this invention and the example which applied the antifouling composition and antifouling film of this invention to the metal-type base material are demonstrated.

Example 1
The antifouling composition produced in Preparation Example 1 was applied to a polypropylene sheet (PP sheet) by an air spray method in an amount such that the dry film thickness was 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. It was. The cured film was peeled from the PP sheet to obtain a single layer film.

Example 2
The antifouling composition produced in Preparation Example 1 was applied to a polypropylene sheet (PP sheet) by an air spray method in an amount such that the dry film thickness was 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. It was. The cured film was peeled from the PP sheet to obtain a single layer film. Thereafter, an acrylic adhesive (Primal N580, manufactured by Rohm & Haas) was applied to the PP sheet side surface at a coating amount of 50 g / m ² and dried to obtain a laminated film.

Example 3
The antifouling composition produced in Preparation Example 1 was applied to a polyethylene terephthalate sheet (PET sheet) by an air spray method in an amount to give a dry film thickness of 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. I let you. Thereafter, an acrylic adhesive (Primal N580, manufactured by Rohm and Haas) was applied to the surface on the PET sheet side at a coating amount of 50 g / m ² and dried to obtain a laminated film.

Example 4
The antifouling composition prepared in Preparation Example 1 was applied to a stainless steel plate by an air spray method so that the dry film thickness was 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours to obtain a laminate. It was.

Example 5
The laminated film produced in Example 2 was attached to a stainless steel plate to obtain a laminated body.

Example 6
The laminated film produced in Example 3 was attached to a stainless steel plate to obtain a laminated body.

Comparative Example 1
The antifouling composition produced in Preparation Example 2 was applied to a polypropylene sheet (PP sheet) by an air spray method in an amount to give a dry film thickness of 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. It was. The cured film was peeled from the PP sheet to obtain a single layer film.

Comparative Example 2
The antifouling composition produced in Preparation Example 2 was applied to a polypropylene sheet by an air spray method in an amount such that the dry film thickness was 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. The cured film was peeled from the PP sheet to obtain a single layer film. Thereafter, an acrylic adhesive (Primal N580, manufactured by Rohm & Haas) was applied to the PP sheet side surface at a coating amount of 50 g / m ² and dried to obtain a laminated film.

Comparative Example 3
The antifouling composition produced in Preparation Example 2 was applied to a polyethylene terephthalate sheet (PET sheet) by an air spray method in an amount to give a dry film thickness of 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours. I let you. Thereafter, an acrylic adhesive (Primal N580, manufactured by Rohm and Haas) was applied to the surface on the PET sheet side at a coating amount of 50 g / m ² and dried to obtain a laminated film.

Comparative Example 4
The antifouling composition prepared in Preparation Example 2 was applied to a stainless steel plate by an air spray method so that the dry film thickness was 30 μm, dried at 80 ° C. for 20 minutes, and then dried at 40 ° C. for 48 hours to obtain a laminate. It was.

Comparative Example 5
The laminated film produced in Comparative Example 2 was attached to a stainless steel plate to obtain a laminated body.

Comparative Example 6
The laminated film produced in Comparative Example 3 was attached to a stainless steel plate to obtain a laminated body.

The following tests were performed on the films and laminates produced as described above.

Oil-based ink contamination test:
Apply the red color of oil-based ink (Magic Ink, registered trademark of Uchida Yoko Co., Ltd.) made by Teranishi Chemical Industry Co., Ltd. to the fluororesin surface of the above film and laminate, leave it for 24 hours, wipe it with a paper towel, and wipe it off. The remaining rate of the area was evaluated according to the following criteria.
A: Less than 5% B: 5-15%
C: Over 15% and 30% or less D: Over 30%

Lacquer contamination test:
Spray the red color of the lacquer spray made by Kansai Paint Co., Ltd., on the fluororesin surface of the film and laminate, leave it for 24 hours, wipe it off with a paper towel, and use the following criteria to determine the remaining percentage of the area that could not be wiped off. evaluated.
A: Less than 5% B: 5-15%
C: Over 15% and 30% or less D: Over 30%

Hair dye solution contamination test:
Apply the black color of Shiseido's hair dyeing solution to the fluororesin surface of the film and laminate with a brush, leave it for 24 hours, wipe it off with a paper towel, and use the following criteria to determine the remaining percentage of the area that cannot be wiped off. It was evaluated with.
A: Less than 5% B: 5-15%
C: Over 15% and 30% or less D: Over 30%

Curry contamination test:
Retort curry made by Otsuka Foods Co., Ltd. was knife-coated on the fluororesin surface of the film and laminate, left for 24 hours, then wiped with a paper towel, and the remaining percentage of the area that could not be wiped was evaluated according to the following criteria. .
A: Less than 5% B: 5-15%
C: Over 15% and 30% or less D: Over 30%

Weather resistance test:
In accordance with JIS K5400, an accelerated weather resistance test was conducted for 500 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), and then the oil-based ink contamination test was conducted.

Contact angle:
Using an automatic contact angle meter Drop Master 701 (manufactured by WA Interface Science Co., Ltd.), the water resistant contact angle of the fluororesin surface of the film and laminate was measured.
A: 100 ° or more B: 90-100 °
C: 80-90 °
D: 80 ° or less

The results are shown in Table 1.

As mentioned above, in the film and laminated body produced in Examples 1-6, with respect to the film and laminated body produced in Comparative Examples 1-6, oil-resistant ink antifouling property (including after a weathering test), All the antifouling indexes including anti-lacquer antifouling properties and anti-fouling properties of hair dyeing solutions gave equivalent or better results. Moreover, according to the film and laminated body produced in Examples 1-6, it turned out that high water repellency is obtained with respect to the film and laminated body produced in Comparative Examples 1-6.

11: Gas stove 12: Smoke 20: Exhaust duct 21: Intake port 22: Main pipe portion 23: Exhaust port 30: Grease filter 40: Range hood

Claims (15)

An antifouling composition for exhaust ducts, grease filters or range hoods, comprising a fluororesin (A) containing a functional group X. The functional group X is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a carbonyl group, a nitrile group, and a hydrolyzable alkyl silicate residue. The antifouling composition for exhaust ducts, grease filters or range hoods according to claim 1. Furthermore, it contains an antifouling component (B),
The antifouling component (B) is at least one component selected from the group consisting of a liquid polydialkylsiloxane (B1) and a liquid fluoropolyether (B2). The antifouling composition for an exhaust duct, grease filter or range hood as described. Polydialkylsiloxane (B1) is a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a thiol _{group, - (C 2 H 4 O} ) a - (C 3 H 6 O) b R 1 (R 1 is C 1 -C And a and b are the same or different and each represents an integer of 1 to 40.), and at least one selected from the group consisting of hydrolyzable alkyl silicate residues The antifouling composition for exhaust ducts, grease filters or range hoods according to claim 3, which contains a functional group. The fluoropolyether (B2) has at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a thiol group, a nitrile group, an iodine atom, and a hydrolyzable alkyl silicate residue. The antifouling composition for exhaust ducts, grease filters or range hoods according to claim 3, which is contained. Furthermore, a curing agent (C) is included,
The curing agent (C) is an isocyanate compound, an amino compound, an epoxy compound, an organic acid, a hydrazide compound, an aziridine compound, a carbodiimide compound, -Si (OR ⁴ ) ₄ (R ⁴ is a non-fluorinated carbonized carbon having 1 to 10 carbon atoms) And a compound containing R ⁵ Si (OR ⁴ ) ₄ (R ⁵ and R ⁶ are the same or different and each represents a non-fluorinated hydrocarbon group having 1 to 10 carbon atoms). The exhaust duct or grease filter according to any one of claims 1 to 5, wherein the exhaust duct and the grease filter are at least one compound selected from the group consisting of: Or the antifouling composition for range hoods. It consists of the coating film formed from the antifouling composition for exhaust ducts, grease filters, or range hoods in any one of Claims 1-6, The antifouling film for exhaust ducts, grease filters, or range hoods characterized by the above-mentioned. An exhaust gas comprising a coating film formed from the exhaust duct, grease filter or anti-fouling composition for a range hood according to any one of claims 1 to 6, and a layer formed from a non-fluorinated polymer. Antifouling film for ducts, grease filters or range hoods. The antifouling film for exhaust ducts, grease filters or range hoods according to claim 8, further comprising an adhesive layer. An exhaust duct, wherein the exhaust duct, grease filter or range hood antifouling composition according to any one of claims 1 to 6 is applied. An exhaust duct comprising the exhaust duct, grease filter, or range hood antifouling film according to claim 7 or 8 attached thereto. A grease filter, to which the exhaust duct, grease filter or range hood antifouling composition according to any one of claims 1 to 6 is applied. 9. A grease filter, characterized in that the exhaust duct, grease filter or range hood antifouling film according to claim 7 or 8 is attached. A range hood, wherein the exhaust duct, the grease filter or the antifouling composition for the range hood according to any one of claims 1 to 6 is applied. A range hood, wherein the exhaust duct, the grease filter or the antifouling film for the range hood according to claim 7 or 8 is attached.

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