JP2022079143A - Water-repellent composition and article using the same - Google Patents

Abstract

To provide a composition capable of forming a film which is excellent in both hardness and water repellency and has a good appearance without coating film cracking.SOLUTION: There is provided a composition containing a copolymer and a fluorine-containing silane compound. The copolymer has a first monomer unit and a second monomer unit. The first monomer unit is a (meth)acrylic monomer unit having no silicon atom. The second monomer unit is a unit derived from a monomer having a silicon atom, which is represented by the following formula (1): CH2=C(R1)-COO-X1-Y1 where R1 represents a hydrogen atom, a fluorine atom or a C1-4 alkyl group; X1 represents a C2-10 divalent organic group optionally containing an ether bond; and Y1 represents a hydrolyzable group containing a silicon atom.SELECTED DRAWING: None

Description

The present invention relates to a water repellent composition and an article using the composition.

For coating the surface of an article, there is a demand for a surface treatment agent capable of forming a film having water repellency and the like. Patent Document 1 discloses a water-repellent oil-repellent antifouling treatment agent containing an acrylate-based copolymer.

Japanese Unexamined Patent Publication No. 2015-187280

On the other hand, in various applications, there is a demand for a surface treatment agent capable of forming a film having excellent hardness and water repellency.

The present invention has been made in view of such a problem, and provides a composition capable of forming a film having excellent hardness and water repellency, and having good appearance without cracking of the coating film.

According to the present invention, the copolymer contains a copolymer and a fluorine-containing silane compound, and the copolymer has a first monomer unit and a second monomer unit, and the first monomer unit. The unit is a (meth) acrylic monomer unit having no silicon atom, and the second monomer unit is a unit derived from a monomer having a silicon atom represented by the following formula (1). can be,
CH ₂ = C (R ¹ ) -COO-X ¹ -Y ¹ (1)
In the above formula (1), R ¹ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ is a divalent organic having 2 to 10 carbon atoms which may contain an ether bond. A composition is provided in which the group, Y1 is ^a hydrolyzable group containing a silicon atom.

As a result of diligent studies, the present inventors have found that when a composition containing a copolymer having a specific composition and a fluorine-containing silane compound is used, both hardness and water repellency are excellent by curing, and the composition is excellent. , It was found that a film having a good appearance can be formed, and the present invention has been completed.

Hereinafter, various embodiments of the present invention will be illustrated. The embodiments shown below can be combined with each other.
Preferably, the fluorine-containing silane compound is at least one selected from the compound group represented by the following formula (2) and the following formula (3).
A-Rf ¹ -B (2)
Rf2 ^- B (3)
In the above equations (2) and (3),
A is a fluorine atom, a hydrogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or B.
B is a group represented by the following formula (4).
-X ² -Y ² (4)
In the above formula (4),
X ² is a divalent organic group having 2 to 6 carbon atoms which may be fluorine-substituted or may contain an ether bond.
Y ² is a hydrolyzable group containing a silicon atom.
Rf ¹ is a poly (oxyperfluoroalkylene) chain represented by the following formula (7), and is a poly (oxyperfluoroalkylene) chain.
-(CF ₂ CF ₂ O) _b (CF (CF ₃ ) CF ₂ O) _c (CF ₂ O) _d (CF ₂ CF ₂ CF ₂ O) _e- (7)
In the above formula (7),
b, c, d and e are independently integers of 0 or 1 or more, and b + c + d + e are 2 to 100, and (CF ₂ CF ₂ O) and (CF (CF ₃ ) CF ₂ O). ), (CF ₂ O), and (CF ₂ CF ₂ CF ₂ O) are not limited in the order of binding, and may be randomly bonded to each other or may be bonded in blocks.
Rf ² is a composition which is a perfluoroalkyl group having 1 to 6 carbon atoms.
Preferably, the second monomer unit is a unit derived from a monomer having a silicon atom represented by the following formula (1-1).
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m -SiR ² _(3-n) (OR ³ ) _n (1-1)
In equation (1-1),
R ¹ is a hydrogen atom, a fluorine atom, or a methyl group.
R ² and R ³ are independent hydrogen atoms or monovalent hydrocarbon groups having 1 to 4 carbon atoms, respectively.
m is an integer of 2 to 4,
n is a composition which is an integer of 1 to 3.
Preferably, the composition contains 0.1 to 20 parts by mass of the fluorine-containing silane compound with respect to 100 parts by mass of the copolymer.
Preferably, the copolymer is a composition having 30 to 90% by mass of the second monomer unit.
Preferably, a fluorine-based solvent and a non-fluorine-based solvent containing no fluorine atom are further contained, and the non-fluorine-based solvent includes a hydrocarbon-based solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent, and a glycol. It is a composition which is at least one selected from the group consisting of a system solvent, a glycol ester system solvent, a glycol ether system solvent, and a glime system solvent.
A composition preferably contains 0.1 to 10 parts by mass of a curing catalyst with respect to 100 parts by mass of the copolymer.
According to another aspect of the present invention, there is provided an article provided with a water-repellent cured film which is a cured product of the above composition.

Hereinafter, embodiments of the present invention will be described. The various features shown in the embodiments shown below can be combined with each other. In addition, the invention is independently established for each characteristic item.

1. 1. Composition The composition according to an embodiment of the present invention contains a copolymer and a fluorine-containing silane compound.

<Copolymer (A)>
The copolymer (A) has a first monomer unit and a second monomer unit. The first monomer unit and the second monomer unit are units constituting the copolymer (A) derived from the first monomer and the second monomer, respectively. The copolymer (A) is synthesized by the copolymerization of the first monomer and the second monomer. The first monomer unit and the second monomer unit are different monomer units. Further, the copolymer (A) may have a monomer unit derived from another monomer copolymerizable with the first monomer and the second monomer.

The copolymer (A) has the first monomer unit in an amount of preferably 10 to 99% by mass, more preferably 10 to 99% by mass, based on 100% by mass of the monomer unit constituting the copolymer (A). It has 70% by mass, more preferably 15 to 60% by mass, and particularly preferably 20 to 55% by mass. Specifically, the content of the first monomer unit in the copolymer (A) is, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70. It is mass% and may be in the range between any two of the numerical values exemplified here.

The copolymer (A) has a second monomer unit in an amount of preferably 1 to 90% by mass, more preferably 30 to 90% by mass, based on 100% by mass of the monomer unit constituting the copolymer (A). It has 90% by mass, more preferably 40 to 85% by mass, and particularly preferably 45 to 80% by mass. When the copolymer (A) contains the second monomer unit in a proportion of 90% by mass or less, cracks during curing of the coating film can be suppressed and the appearance of the cured film is excellent. When the copolymer (A) contains the second monomer unit in a proportion of 10% by mass or more, the hardness of the cured film is excellent. Specifically, the content of the second monomer unit in the copolymer (A) is, for example, 30,35,40,45,50,55,60,65,70,75,80,85,90. It is mass% and may be in the range between any two of the numerical values exemplified here.

<First monomer unit>
The first monomer unit is a (meth) acrylic monomer unit having no silicon atom. The (meth) acrylic monomer unit having no silicon atom preferably has neither a silicon-carbon bond nor a silicon-oxygen bond, and more specifically, an oxysilyl group such as an alkoxysilyl group and a silanol group. I don't have it. By using such a first monomer unit together with the second monomer unit, the hardness of the cured film is excellent, cracks during curing can be suppressed, and the appearance of the cured film is excellent.

The first monomer unit is preferably a (meth) acrylic acid ester monomer unit, and more preferably a methacrylic acid ester monomer unit. Further, in one embodiment, the first monomer unit is preferably a monomer unit derived from a monofunctional (meth) acrylic acid ester monomer having one acryloyloxy group.

Specific examples of the first monomer from which the first monomer unit is derived include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl. (Meta) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate , Cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, decyl ( Meta) acrylate, Isodecyl (meth) acrylate, Undecyl (meth) acrylate, Lauryl (meth) acrylate, Cetyl (meth) acrylate, Stearyl (meth) acrylate, Isostearyl (meth) acrylate, Behenyl (meth) acrylate, Isobornyl (meth) ) Acrylate, 2-phenoxyethyl (meth) acrylate, 3,5,5-trimethylcyclohexane acrylate, p-cumylphenol EO modified (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate , Dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 2-ethyladamantyl (meth) acrylate and the like. Further, hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, hydroxybutyl (meth) acrylates, and glycerol (meth) acrylates having hydrophilic groups and organic functional groups, and (meth). Acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropylphthalic acid , 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, crotonic acid, fumaric acid , Maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate and other carboxyl group-containing monomers, maleic anhydride, itaconic acid anhydride and other acid anhydride group-containing monomers, glycidyl (meth) acrylate, glycidyl α-ethylacrylate. , (Meta) acrylic acid 3,4-epoxybutyl and other epoxy group-containing monomers, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and other amino group-containing (meth) acrylic acid ester-based monomers, (meth) Amides such as acrylamide, Nt-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone acrylamide, maleic acid amide, and maleimide. Examples thereof include a monomer containing a group, a heterocyclic basic monomer such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole. In addition, perfluorohexyl ethyl (meth) acrylate, perfluorohexyl (meth) acrylate, perfluoropentylpropyl (meth) acrylate, perfluoropentylethyl (meth) acrylate, and perfluorobutyl ethyl (meth) having a perfluoroalkyl group. ) Acrylic, Perfluorobutylmethyl (meth) acrylate, Perfluoropropylethyl (meth) acrylate, Perfluoropropylmethyl (meth) acrylate, Perfluoroethylethyl (meth) acrylate, Perfluoroethylmethyl (meth) acrylate, Trifluoro Ethyl (meth) acrylate and the like can be mentioned. Among them, the first monomer is preferably (meth) acrylic acid ester, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and particularly preferably methyl (meth) acrylate. Meta) acrylate. These may be used alone or in combination of two or more.

The first monomer unit is preferably a structural unit having 10 or less carbon atoms, and more preferably a structural unit having 6 or less carbon atoms. The first monomer unit is preferably a monomer unit derived from a monomer having a molecular weight of 200 or less, and more preferably a monomer unit derived from a monomer having a molecular weight of 150 or less. , More preferably, it is a monomer unit derived from a monomer having a molecular weight of 110 or less.

<Second monomer unit>
The second monomer unit is a monomer unit derived from the monomer represented by the following formula (1) (second monomer). By using such a second monomer unit together with the first monomer unit, the hardness of the cured film is excellent, cracks during curing can be suppressed, and the appearance of the cured film is excellent.
CH ₂ = C (R ¹ ) -COO-X ¹ -Y ¹ (1)

In the above formula (1), R ¹ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. X ¹ is a divalent organic group having 2 to 10 carbon atoms which may contain an ether bond. Y ¹ is a hydrolyzable group containing a silicon atom.

X ¹ is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms. Further, Y ¹ is a hydrolyzable group containing a silicon atom and an alkoxy group. The second monomer having such a preferable structure is, for example, a monomer represented by the following formula (1-1).
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m -SiR ² _(3-n) (OR ³ ) _n (1-1)

In the above formula (1-1), R ¹ is a hydrogen atom, a fluorine atom, or a methyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. R ² and R ³ are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group. m is an integer of 2 to 4, preferably 3. n is an integer of 1 to 3, preferably 2 to 3, and more preferably 3.

The second monomer unit is, in one embodiment, preferably a monomer unit having no cyclic structure. Further, in one embodiment, the second monomer unit is preferably a monomer unit having no fluorine atom.

Specific examples of the second monomer from which the second monomer unit is derived include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. , 3-Methyloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and other monomer units derived from (meth) acrylic monomers. Among them, the second monomer is preferably 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or 3-methacryloxypropyltriethoxysilane. It is a derived monomer unit, and is particularly preferably 3-methacryloxypropyltrimethoxysilane. These may be used alone or in combination of two or more.

The second monomer unit is preferably a structural unit having 7 or more carbon atoms, and more preferably a structural unit having 10 or more carbon atoms. The second monomer unit is preferably a structural unit having 20 or less carbon atoms, and more preferably a structural unit having 15 or less carbon atoms. The second monomer unit is preferably a monomer unit derived from a monomer having a molecular weight of 200 or more, and more preferably a monomer unit derived from a monomer having a molecular weight of 220 or more. .. The second monomer unit is preferably a monomer unit derived from a monomer having a molecular weight of 400 or less, more preferably a simpler derived from a monomer having a molecular weight of 300 or less. It is a molecular weight unit.

<Other monomer units>
Examples of the first monomer and other monomers copolymerizable with the second monomer include styrene, t-butylstyrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonityl, vinyl acetate, and the like. Examples thereof include various vinyl-based monomers such as vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, and alkyl vinyl monomer.

<Fluorine-containing silane compound (B)>
The fluorine-containing silane compound (B) is a silane compound containing a fluorine atom. The fluorine-containing silane compound (B) may contain a partially hydrolyzed compound.

The fluorine-containing silane compound is, for example, at least one selected from the compound group represented by the following formula (2) and the following formula (3). These may be used alone or in combination of two or more.
A-Rf ¹ -B (2)
Rf2 ^- B (3)

In the above formulas (2) and (3), A is a fluorine atom, a hydrogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or B. B is a group represented by the following formula (4).
-X ² -Y ² (4)

In the above formula (4), X ² is a divalent organic group having 2 to 6 carbon atoms which may be substituted with fluorine or may contain an ether bond. X ² is preferably a linking group represented by the following formulas (5-1) to (5-3), for example.
-CF ₂ CH ₂ OCH ₂ CH ₂ CH _2- (5-1)
-CF ₂ CH ₂ CH ₂ CH _2- (5-2)
-CF (CF ₃ ) CH ₂ OCH ₂ CH ₂ CH _2- (5-3)

In the above formula (4), Y ² is a hydrolyzable group containing a silicon atom. Y ² is preferably a group having a structure represented by the following formula (6), for example.
-SiR ⁴ _(3-r) (OR ⁵ ) _r (6)

R ⁴ and R ⁵ are independently hydrogen atoms or monovalent hydrocarbon groups having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and more preferably a methyl group. r is an integer of 1 to 3, preferably 2 to 3, and more preferably 3.

Rf ¹ is a repeating unit of (CF ₂ CF ₂ O) (hereinafter, also referred to as a repeating unit (CF ₂ CF ₂ O)) and a repeating unit of (CF (CF ₃ ) CF ₂ O) (hereinafter, a repeating unit (hereinafter, repeating unit (hereinafter, repeated unit)). CF (CF ₃ ) CF ₂ O)), (CF ₂ O) repeating unit (hereinafter also referred to as repeating unit (CF ₂ O)), and (CF ₂ CF ₂ CF ₂ O) repeating unit. It consists of at least one selected from the group consisting of (hereinafter, also referred to as a repeating unit (CF ₂ CF ₂ CF ₂ O)). Rf ¹ is, for example, a linking group of a poly (oxyperfluoroalkylene) chain represented by the following formula (5).
-(CF ₂ CF ₂ O) _b (CF (CF ₃ ) CF ₂ O) _c (CF ₂ O) _d (CF ₂ CF ₂ CF ₂ O) _e- (7)

In the above formula (7), b, c, d and e are independently integers of 0 or 1 or more, and b + c + d + e is 2 to 100. b + c + d + e is more preferably 2 to 80, and particularly preferably 2 to 50. When b + c + d + e is in the above range, the water repellency and the solubility in a non-fluorine solvent are improved. The values of b, c, d and e in the composition are average values, respectively.

In Rf ¹ , the order of joining the repeating unit (CF ₂ CF ₂ O), the repeating unit (CF (CF ₃ ) CF ₂ O), the repeating unit (CF ₂ O), and the repeating unit (CF ₂ CF ₂ CF ₂ O). Are not limited, and may be randomly combined with each other or may be combined with each other in blocks.

As Rf ¹ , for example, a linking group represented by the following formulas (7-1) to (7-5) (hereinafter, also referred to as a linking group (7-1) to a linking group (7-5)) is used. Can be mentioned.
-(CF ₂ CF ₂ O) _b1- (7-1)
However, b1 is an integer of 5 to 80.
-(CF (CF ₃ ) CF ₂ O) _c1- (7-2)
However, c1 is an integer of 5 to 55.
-(CF ₂ CF ₂ CF ₂ O) _e1- (7-3)
However, e1 is an integer of 5 to 55.
-(CF ₂ CF ₂ O) _b2- (CF ₂ O) _d1- (7-4)
However, b2 is an integer of 1 to 50, and d1 is an integer of 1 to 50.
-(CF (CF ₃ ) CF ₂ O) _c2- (CF ₂ O) _d2- (7-5)
However, c2 is an integer of 1 to 40, and d2 is an integer of 1 to 40.

Of these, a linking group (7-1), a linking group (7-3) or a linking group (7-4) is preferable. In the linking group (7-1), b1 is more preferably 6 to 60, and particularly preferably 10 to 40. In the linking group (7-3), e1 is more preferably 5 to 50, and particularly preferably 8 to 30. In the linking group (7-4), b2 is preferably 1 to 30 and d1 is preferably 1 to 30.

Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms.

The composition contains the fluorosilane compound (B) in an amount of preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, still more preferably 2 to 2 to 100 parts by mass of the copolymer (A). Contains 13 parts by mass. Within such a range, both the hardness and water repellency of the cured film are excellent. The content of the fluorine-containing silane compound (B) is, specifically, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, with respect to 100 parts by mass of the copolymer (A). 7,8,9,10,11,12,13,14,15,16,17,18,19,20 parts by mass, even if it is within the range between any two of the numerical values exemplified here. good.

<Fluorine solvent (C)>
The composition according to one embodiment of the present invention may further contain a fluorinated solvent. The fluorine-based solvent (C) is, for example, a fluorine-based solvent such as a hydrocarbon having a fluorine atom.

The fluorinated solvent contains, for example, fluorine and carbon, and may further contain chlorine, oxygen and hydrogen. Specific examples of the fluorinated solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, fluoroalcohols and the like.

As the fluorinated alkane, a compound having 4 to 8 carbon atoms is preferable. Examples of the fluorinated alkane include CF ₃ CH ₂ CF ₂ H (HFC-245fa), CF ₃ CH ₂ CF ₂ CH ₃ , perfluorohexane, 1H-perfluorohexane, perfluorooctane, C ₆ F ₁₃ H, C ₆ F. ₁₃ C ₂ H ₅ , C ₂ F ₅ CHFCHFCF ₃ and the like can be mentioned.

Examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, and bis (trifluoromethyl) benzene. As the fluoroalkyl ether, a compound having 4 to 12 carbon atoms is preferable. Examples of the fluoroalkyl ether include CF ₃ CH ₂ OCF ₂ CF ₂ H, C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ and the like. ..

Examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine. Examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like. Other examples include dichloropentafluoropropane and perfluoro (2-butyltetrahydrofuran). These fluorine-based solvents may be used alone or in combination of two or more.

<Non-fluorine solvent (D)>
The composition according to one embodiment of the present invention may further contain a non-fluorinated solvent (D). The non-fluorine-based solvent (D) is a compound that does not contain a fluorine atom. In one embodiment, the non-fluorinated solvent (D) preferably has at least one selected from an ether structure, a hydroxyl group, a glycol-derived structure, a carbonyl group, and the like. In one embodiment, the non-fluorinated solvent (D) preferably has an ether structure and a hydroxyl group. By adding the non-fluorine-based solvent (D) having such a structure, the water repellency of the cured film is particularly excellent.

The composition according to one embodiment of the present invention may contain, for example, as the non-fluorine-based solvent (D), a hydrocarbon-based solvent, an alcohol-based solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent, a glycol-based solvent, and a glycol. It may contain at least one selected from the group consisting of an ester solvent, a glycol ether solvent and a glime solvent.

Examples of the hydrocarbon solvent include toluene, xylene, solventnaphtha, normal hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, normal heptane, isooctane, normal decane, normal pentane, isopentan and the like.

Examples of the alcohol-based solvent include methanol, ethanol, denatured ethanol, butanol, isobutanol, isopropyl alcohol, normal propyl alcohol, tertiary butanol, secondary butyl alcohol, 1,3-butanediol, 1,4-butanediol, and 2. -Ethylhexanol, benzyl alcohol and the like can be mentioned.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, diacetone alcohol and the like.

Examples of the ester solvent include ethyl acetate, methyl acetate, butyl acetate, secondary butyl acetate, amyl acetate, normal propyl acetate, isopropyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.

Examples of the ether solvent include diisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane, and methyl tertiary butyl ether.

Examples of the glycol-based solvent include ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol.

Examples of the glycol ester solvent include ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl ether acetate.

Examples of the glycol ether-based solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, methylmethoxybutanol, and dipropylene. Glycolmethyl ether and the like can be mentioned.

Examples of the glyme-based solvent include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.

In one embodiment, the non-fluorine solvent (D) is preferably diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether, ethylene. Glycol monomethyl ether, butyl acetate, cyclohexanone, methylcyclohexane and the like.

The molecular weight of the non-fluorinated solvent (D) is preferably 30 g / mol to 200 g / mol, preferably 80 g / mol to 180 g / mol. The boiling point of the additive (D) is preferably 50 to 270 ° C, preferably 100 to 260 ° C. Within such a range, the water repellency of the cured film can be improved.

The composition contains the non-fluorine solvent (D) in an amount of preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the copolymer (A). Further, the composition contains the non-fluorine solvent (D) in an amount of preferably 0.1 to 20% by mass, more preferably 1 to 16% by mass, based on 100% by mass of the composition. Within such a range, the water repellency of the cured film is particularly excellent, and the influence of the non-fluorine-based solvent (D) on the appearance can be suppressed. If the amount of the non-fluorine-based solvent (D) added is too large, uniform coating becomes difficult and unevenness is likely to occur in the coating film. Specifically, the content of the additive (D) in the composition containing the non-fluorinated solvent (D) is, for example, 0.1, 0.5, 1, 3, 4, 5, 6, 7, 8. , 9,10,11,12,13,14,15,16,17,18,19,20% by mass, and may be within the range between any two of the numerical values exemplified here.

<Curing catalyst (E)>
The composition according to one embodiment of the present invention may further contain a curing catalyst from the viewpoint of promoting the condensation reaction of the copolymer (A) and the fluorine-containing silane compound (B).

As the curing catalyst (E), various conventionally known hydrolysis / condensation catalysts can be used. Specifically, the following can be exemplified. That is, acids such as hydrochloric acid, nitrate, sulfuric acid, phosphoric acid, acetic acid, maleic acid and methanesulphonic acid, amine compounds such as NaOH, ammonia, triethylamine, dibutylamine, hexylamine, octylamine and dibutylamine, and salts of amine compounds. , Basics such as quaternary ammonium salts such as benzyltriethylammonium chloride and tetramethylammonium hydroxide, fluoride salts such as potassium fluoride and sodium fluoride, solid acidic catalysts or solid basic catalysts (eg ion exchange resins). (Catalyst, etc.), metal salts of organic carboxylic acids such as iron-2-ethylhexoate, titanium naphthate, zinc stearate, dibutyltin diacetate, titanium diisopropoxybis (ethylacetoacetate) tetrabutoxytitanium, tetra- Organic titanium esters such as i-propoxytitanium, dibutoxy- (bis-2,4-pentandionate) titanium, di-i-propoxy (bis-2,4-pentandionate) titanium, tetrabutoxyzirconium, tetra-i -Propoxizylzyl, dibutoxy- (bis-2,4-pentandionate) zirconium, di-i-propoxy (bis-2,4-pentandionate) organic zirconium esters such as zirconium, alkoxy such as aluminum triisopropoxide Organic metal compounds such as aluminum compounds and aluminum chelate compounds such as aluminum acetylacetonate complexes, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxy Aminoalkyl-substituted alkoxysilanes such as silane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane are exemplified, and these may be used alone or in combination. Further, these catalysts may be blended with the present antifouling coating agent at the time of coating for the purpose of obtaining a dense and strong cured film. Of these, organometallic compounds containing aluminum and titanium are preferable from the viewpoint of solubility in a fluorine-based solvent and curability. More specifically, an aluminum chelate compound (for example, DX9740 (manufactured by Shin-Etsu Chemical Co., Ltd.)), an organic titanium-based compound (for example, Organtics TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)) and the like are preferable.

The composition contains the curing catalyst (E) in an amount of preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the copolymer (A). Specifically, the content of the curing catalyst (E) with respect to 100 parts by mass of the copolymer (A) is, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, It is 5, 6, 7, 8, 9, and 10, and may be within the range between any two of the numerical values exemplified here.

<Other additives>
The composition may contain other additives as needed. Other additives include, for example, pigments such as titanium dioxide, inorganic or organic fillers, film-forming aids, plasticizers, antifreeze agents, preservatives, fungicides, antibacterial agents, antifoaming agents, dispersants. , Thickeners, leveling agents, pH adjusters, fibers, matting agents, ultraviolet absorbers, antioxidants, light stabilizers and the like can be mixed.

<Preparation method of composition>
In the composition, the copolymer (A) and the fluorine-containing silane compound (B) are dissolved in the fluorine-based solvent (C), and the mixture is optionally mixed with the non-fluorine-based solvent (D) and the curing catalyst (E). Etc. can be added.

2. 2. Cured film and article The composition according to the present invention can be used, for example, as a water-repellent surface treatment agent for forming a water-repellent film for various articles. Further, it is preferable that the composition forms a cured product by thermosetting.

The article according to an embodiment of the present invention is a water-repellent article provided with a base material and a water-repellent cured film provided on the base material. The water-repellent cured film is a cured film of the above composition. The cured film of the surface treatment agent is obtained by applying the composition to the surface of the substrate and curing it.

As a coating method for applying the composition to the surface of the substrate, a hand coating method, a nozzle flow coating method, a dipping method, a spray method, a reverse coating method, a flow coating method, a spin coating method, and a roll coating method can be appropriately adopted. Among these coating methods, the hand coating method is preferable because it has high coating efficiency and low coating loss, and can reduce the introduction cost of coating equipment. In the present invention, the "hand-painting method" is a means for bringing the composition into contact with the substrate after supplying the composition to the coating member, and the member after supplying the composition to the substrate. Refers to a technical means for applying a coating liquid onto a substrate by at least one means selected from the means for spreading the composition. Examples of the member to which the composition is supplied or the member to which the composition is spread include cloth, paper, non-woven fabric, gauze, sponge, felt and the like. The means for bringing the member to which the coating liquid has been supplied into contact with the base material, or the means for stretching the coating liquid with the member may be a manual method, a robot, a machine, or the like.

The water-repellent article can be obtained by, for example, curing at room temperature to 100 ° C. after application of the composition. It can be cured even at room temperature and does not necessarily require heating, but by heating, the silanol groups and the binding groups such as hydroxyl groups present on the surface of the substrate are stronger than those without heat treatment. Can be combined. Due to this strong bond, a film (water repellent layer) having excellent durability can be formed on the surface of the base material. The heating may be carried out under normal pressure, under pressure, under reduced pressure, or under an inert atmosphere. The silanol group is derived from a hydrolyzate contained in a copolymer or a fluorine-containing silane compound and a newly hydrolyzed hydrolyzate. The room temperature means, for example, 10 to 30 ° C. in one embodiment.

When the excess of the composition becomes a dry substance and remains on the substrate, the excess can be wiped off with a paper towel or cloth moistened with an organic solvent or water, or a dry paper towel or cloth.

<Base material>
The base material to which the surface treatment agent is applied is not particularly limited as long as it has a heat resistant temperature higher than the curing treatment temperature. As the base material, for example, flat glass, plastic, or metal usually used for window glass for vehicles and window glass for buildings can be used. Reflective base materials such as mirrors formed using these flat glass sheets, frosted glass, glass with a pattern, and the like can be used. In addition to the glass base material, base materials made of ceramic materials used for tiles, roof tiles, sanitary ware, tableware and the like, frames such as glass windows, cookers, sinks, painted surfaces of automobile bodies and the like can be mentioned.

Further, a treatment for improving the adhesive strength between the base material and the water-repellent coating can be performed on the surface of the base material in advance. Such treatment includes polishing / cleaning / drying with various polishing solutions, surface modification treatment with an acidic solution or a basic solution, primer treatment, plasma irradiation, corona discharge, high-pressure mercury lamp irradiation, and the like to activate active groups on the surface of the substrate. Can be mentioned. In particular, the primer treatment for forming a thin film containing silicate is preferable because the number of silanol groups (active groups) on the surface to which the surface treatment agent is applied can be increased.

Hereinafter, the present invention will be described in more detail with reference to examples. Moreover, these are merely examples and do not limit the content of the present invention.

<Synthesis of copolymer (A)>
The abbreviations of the monomers described in the synthesis example are as follows.
MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation)
KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
C1FMA: 2,2,2-trifluoroethyl methacrylate (manufactured by Toso Finechem)
IBXMA: Isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
C6FMA: 2-Perfluorohexyl ethyl methacrylate (manufactured by Daikin Corporation)
BzMA: Benzyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
MDMA: 2-Methyladamantyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

(Copolymer A-1)
100 g of MMA, 300 g of KBM-503, 408 g of bis (trifluoromethyl) benzene as a reaction solvent, as a polymerization initiator in a 1000 mL separable flask equipped with a stirrer, a reflux cooler, a thermometer, and a dry nitrogen introduction tube. It contained 8 g of 2,2-azobisisobutyronitrile and polymerized at 80 ° C. for 8 hours in a nitrogen atmosphere. The weight average molecular weight of the copolymer was about 50,000. The weight average molecular weight is a polystyrene-equivalent value measured by a gel permeation chromatography method (GPC method).

(Copolymer A-2)
It was synthesized by the same method as in (A-1) except that 200 g of MMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 43,000.

(Copolymer A-3)
It was synthesized by the same method as in (A-1) except that 100 g of C1FMA, 100 g of IBXMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 58,000.

(Copolymer A-4 :)
It was synthesized by the same method as in (A-1) except that 100 g of C6FMA, 100 g of IBXMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 57,000.

(Copolymer A-5)
It was synthesized by the same method as in (A-1) except that 200 g of IBXMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 57,000.

(Copolymer A-6)
It was synthesized by the same method as in (A-1) except that 200 g of C1FMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 45,000.

(Copolymer A-7)
It was synthesized by the same method as in (A-1) except that 100 g of C1FMA and 300 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 51,000.

(Copolymer A-8)
It was synthesized by the same method as in (A-1) except that 100 g of BzMA and 300 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 55,000.

(Copolymer A-9)
It was synthesized by the same method as in (A-1) except that 200 g of MDMA and 200 g of KBM-503 were used as monomers. The weight average molecular weight of the copolymer was about 100,000.

(Copolymer A-10)
It was synthesized by the same method as in (A-1) except that 400 g of KBM-503 was used as a monomer. The weight average molecular weight of the copolymer was about 59,000.

(Copolymer A-11)
It was synthesized by the same method as in (A-1) except that 160 g of C1FMA and 240 g of C6FMA were used as monomers. The weight average molecular weight of the copolymer was about 51,000.

(Copolymer A-12)
It was synthesized by the same method as in (A-1) except that 80 g of C1FMA, 240 g of C6FMA and 80 g of IBXMA were used as monomers. The weight average molecular weight of the copolymer was about 49,000.

<Fluorine-containing silane compound (B)>
(B-1), (B-2), and (B-3) were synthesized by the raw materials and methods described in Synthesis Example 5, Synthesis Example 1, and Synthesis Example 8 of Patent No. 6758725, respectively. A commercially available product was used for B-4.
B-1: CF ₃ CF ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ O) ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
B-2: CF ₃ CF ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ O) ₂ CF ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
B-3: (CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ OCH ₂ CF ₂ O (CF ₂ CF ₂ O) _p (CF ₂ O) _q CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
p / q = 0.8 to 1.0, p + q ≒ 45
B-4: C ₆ F ₁₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃

As B-4, a commercially available trimethoxy (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Fluorine solvent (C)>
Bis (trifluoromethyl) benzene (MTF-TFM: manufactured by Central Glass Co., Ltd.)
Asahi Clean AE-3000 (manufactured by AGC)

<Non-fluorine solvent (D)>
Diethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 162.2 g / mol, boiling point: 230 ° C]
Triethylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 164.2 g / mol, boiling point: 248 ° C]
Diethylene glycol monobutyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 204.3 g / mol, boiling point: 247 ° C]
Diethylene glycol monoethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 176.2 g / mol, boiling point: 218 ° C]
Propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 132.2 g / mol, boiling point: 146 ° C]
Ethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 118.2 g / mol, boiling point: 171 ° C]
Ethylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 76.1 g / mol, boiling point: 124 ° C]
Butyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 116.2 g / mol, boiling point: 126 ° C]
Cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 98.2 g / mol, boiling point: 157 ° C]
Methylcyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) [Molecular weight: 98.2 g / mol, boiling point: 100 ° C]

<Curing catalyst (E)>
E-1: DX9740 (manufactured by Shin-Etsu Chemical Co., Ltd.)
E-2: TC750 (Organics TC-750: manufactured by Matsumoto Fine Chemical Co., Ltd.)
E-3: U100 (Neostan U100: manufactured by Nitto Kasei Co., Ltd.)

<Adjustment of composition>
Polymer A-1 is 16.0 g, DX-9740 (manufactured by Shin-Etsu Chemical Co., Ltd.) is 0.2 g, Organix TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.) is 0.2 g, and fluorine-containing silane compound B-2 is 0.24 g. , 13.4 g of bis (trifluoromethyl) benzene, 50.0 g of asahiclin AE-3000, and 3 g of triethylene glycol monomethyl ether were weighed and uniformly mixed to prepare a surface treatment agent.

<Creation of water-repellent cured film>
(Preparation of base material)
The surface of the slide glass (26 x 76 mm) was washed with purified water, dried, and then wiped dry with a non-woven fabric (Bencot) to prepare a base material.

(Making water-repellent glass)
The slide glass was dip-coated on 80 mL of the prepared surface treatment agent and air-dried for 5 minutes. Then, the coating film was cured under the curing conditions shown in Table 2 to obtain a water-repellent cured film.

<Evaluation of water-repellent cured film>
Each evaluation item was evaluated by the following method.

(1) Pencil hardness According to JIS K5600-5-4, the pencil hardness on the coating film surface side was measured under a load condition of 500 g using "Uni" manufactured by Mitsubishi Pencil Co., Ltd. as a pencil.

(2) Water Contact Angle Using a contact angle meter (LSE-B100W manufactured by NICK), 2 μL of water droplets were generated, and the contact angle with respect to the water-repellent glass was measured. The measurement was performed at 5 different points on the surface, and the average value was shown.

(3) Appearance evaluation Evaluation was made according to the following evaluation criteria.
◯: No visual defects such as paint film cracks / cracks ×: Visually visual defects such as paint film cracks / cracks

The evaluation results are shown in Tables 2 to 6 for the combination of each component and each curing condition.

From the above results, a cured film having high hardness and high water repellency can be obtained when a composition containing the copolymer (A) having a predetermined combination of monomer units and the fluorine-containing silane compound (B) is used. I was able to. Further, when the additive (D) was further contained, the water repellency was improved.
On the other hand, in Comparative Example 1 and Comparative Example 2, a copolymer composed of a monomer containing a fluorine atom, which is expected to be water repellent, was used, but the hardness was not sufficient (less than "HB"). Further, in Comparative Example 3, when a copolymer containing only a monomer having a silicon atom was used without using a (meth) acrylic monomer having no silicon atom, the hardness was relatively high and water repellency was also exhibited. However, the film cracked during curing. Cracks and the like spoil the appearance of the surface-treated article and are not suitable for use. In Comparative Example 4, since the fluorine-containing silane compound was not contained, the water repellency was not sufficient (less than 90 °).

The article provided with the water-repellent cured film treated with the surface treatment agent of the present invention has good water repellency, pencil hardness and appearance, and is a repair agent for the exterior and interior of transport aircraft such as automobiles, ships and aircraft, or a kitchen. It can be used for parts that require water repellency and durability in protective films such as bathrooms, outer walls, flat glass, and displays.

Claims (8)

Containing a copolymer and a fluorine-containing silane compound,
The copolymer has a first monomer unit and a second monomer unit.
The first monomer unit is a (meth) acrylic monomer unit having no silicon atom, and is a unit.
The second monomer unit is a unit derived from a monomer having a silicon atom represented by the following formula (1).
CH ₂ = C (R ¹ ) -COO-X ¹ -Y ¹ (1)
In the above formula (1),
R ¹ is a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
X ¹ is a divalent organic group having 2 to 10 carbon atoms which may contain an ether bond.
Y ¹ is a composition which is a hydrolyzable group containing a silicon atom. The fluorine-containing silane compound is at least one selected from the compound group represented by the following formula (2) and the following formula (3).
A-Rf ¹ -B (2)
Rf2 ^- B (3)
In the above equations (2) and (3),
A is a fluorine atom, a hydrogen atom, a perfluoroalkyl group having 1 to 6 carbon atoms, or B.
B is a group represented by the following formula (4).
-X ² -Y ² (4)
In the above formula (4),
X ² is a divalent organic group having 2 to 6 carbon atoms which may be fluorine-substituted or may contain an ether bond.
Y ² is a hydrolyzable group containing a silicon atom.
Rf ¹ is a poly (oxyperfluoroalkylene) chain represented by the following formula (7), and is a poly (oxyperfluoroalkylene) chain.
-(CF ₂ CF ₂ O) _b (CF (CF ₃ ) CF ₂ O) _c (CF ₂ O) _d (CF ₂ CF ₂ CF ₂ O) _e- (7)
In the above formula (7),
b, c, d and e are independently integers of 0 or 1 or more, and b + c + d + e are 2 to 100, and (CF ₂ CF ₂ O) and (CF (CF ₃ ) CF ₂ O). ), (CF ₂ O), and (CF ₂ CF ₂ CF ₂ O) are not limited in the order of binding, and may be randomly bonded to each other or may be bonded in blocks.
Rf ² is a perfluoroalkyl group having 1 to 6 carbon atoms.
The composition according to claim 1. The second monomer unit is a unit derived from a monomer having a silicon atom represented by the following formula (1-1).
CH ₂ = C (R ¹ ) -COO- (CH ₂ ) _m -SiR ² _(3-n) (OR ³ ) _n (1-1)
In equation (1-1),
R ¹ is a hydrogen atom, a fluorine atom, or a methyl group.
R ² and R ³ are independent hydrogen atoms or monovalent hydrocarbon groups having 1 to 4 carbon atoms, respectively.
m is an integer of 2 to 4,
n is an integer of 1 to 3,
The composition according to claim 1 or 2. The composition according to any one of claims 1 to 3, which contains 0.1 to 20 parts by mass of the fluorine-containing silane compound with respect to 100 parts by mass of the copolymer. The composition according to any one of claims 1 to 4, wherein the copolymer has 30 to 90% by mass of the second monomer unit. Further containing a fluorine-based solvent and a non-fluorine-based solvent containing no fluorine atom,
The non-fluorosolvent is composed of a group consisting of a hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ester solvent, an ether solvent, a glycol solvent, a glycol ester solvent, a glycol ether solvent, and a glime solvent. The composition according to any one of claims 1 to 5, which is at least one selected. The composition according to any one of claims 1 to 6, which contains 0.1 to 10 parts by mass of a curing catalyst with respect to 100 parts by mass of the copolymer. An article comprising a water-repellent cured film which is a cured product of the composition according to any one of claims 1 to 7.