JP2022107653A - Coating modifier, and coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition for adding excellent antifouling property to a substrate.

SOLUTION: There is provided a coating modifier containing a fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer represented by (a) formula:CH₂=C(-X)-C(=O)-Y-Z-Rf, wherein X is a hydrogen atom, a monovalent organic group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a bivalent organic group, Rf is a perfluoroalkyl group having 1 to 6 carbon atoms, and a repeating unit derived from a non-fluorine monomer which is a (meth)acrylate ester monomer represented by (b) formula:CH₂=CA¹¹-C(=O)-O-A¹², wherein A¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a halogen atom other than a fluorine atom, and A¹² is a hydrocarbon group having 1 to 40 carbon atoms.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

TECHNICAL FIELD The present disclosure relates to a paint modifier (paint additive) comprising a fluoropolymer containing a fluoromonomer having a fluoroalkyl group. The present disclosure also relates to paint compositions comprising paint modifiers and paints.

Conventionally, various paint compositions or paint additives have been proposed to protect buildings such as bridges from the environment.

Patent Document 1 (Japanese Patent Publication No. 2001-524573) and Patent Document 2 (Japanese Patent Publication No. 2001-524559) disclose a coating composition comprising an acrylic polymer and a fluoroalkyl group-containing polymer.
Patent Document 3 (Japanese National Publication of International Patent Application No. 2013-531708) discloses a coating composition containing a fluoropolymer containing a vinylidene chloride repeating unit and an EO chain.
Patent Document 4 (JP-A-10-168140) contains a copolymer containing a structural unit derived from a fluoroalkyl group-containing (meth)acrylic acid ester and a structural unit derived from a polyalkylene glycol (meth)acrylate. It discloses a paint additive comprising:

Patent Document 5 (Japanese Patent Application Laid-Open No. 6-240201) discloses a technique of adding a fluoropolymer having a fluoroalkyl group having 8 carbon atoms to a powder coating to impart ink stain resistance, leveling performance, and water and oil repellency. is disclosed.

Japanese Patent Publication No. 2001-524573 Japanese Patent Publication No. 2001-524559 Japanese Patent Publication No. 2013-531708 JP-A-10-168140 JP-A-6-240201

An object of the present disclosure is to provide a coating composition that imparts excellent antifouling properties to substrates (eg, structures such as bridges).

This disclosure is
a) Formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. ]
and (b) a fluoropolymer having repeating units derived from a non-fluorinated monomer having a hydrocarbon group. offer.

The non-fluorine monomer (b) has the formula:
_CH2 = ^CA11 -C(=O) ^-OA12
[In the formula, A ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a is a halogen atom,
A ¹² is a hydrocarbon group having 1 to 40 carbon atoms. ]
It is preferably a (meth)acrylate ester monomer represented by.

In addition, the present disclosure provides
Provided is a coating composition comprising (1) a coating modifier comprising a fluoropolymer, and (2) a coating comprising a resin.
Additionally, the present disclosure provides a paint comprising polymerizing monomer (a) and monomer (b) to obtain a fluoropolymer and then mixing the fluoropolymer with a paint. A method of making a composition is provided.

Further, the present disclosure provides a method of coating a substrate, comprising applying the coating composition to the surface of the substrate to form a coating film to impart antifouling properties to the substrate.
Additionally, the present disclosure provides a coating composition film formed by applying the coating composition to the surface of a substrate.

According to the present disclosure, a coating film having excellent antifouling properties is formed. The antifouling property means that it is difficult for dirt to adhere (excellent resistance to dirt adhesion) and that even if dirt adheres, it can be easily removed (excellent dirt releasability). That is, dirt (eg, salt, algae, soil, and carbon) is less likely to adhere to the coating film surface, and even if dirt adheres to the coating film surface, it is easily removed. In particular, it has high antifouling properties against salts such as sodium chloride. For example, substrates (eg, metal, concrete and wood) submerged in seawater are well protected from seawater by the coating film, preventing salt damage. The present disclosure can also provide coating compositions with excellent mar resistance.
According to the present disclosure, the substrate is well protected. In particular, metals such as steel plates are effectively prevented from rusting.

The coating composition comprises (1) a coating modifier, and (2) a coating.

(1) Paint Modifier The paint modifier contains a fluoropolymer. Generally, paint modifiers are solutions comprising or consisting of fluoropolymers and organic solvents.
The fluoropolymer is a copolymer having repeating units derived from the fluoromonomer (a) and repeating units derived from the non-fluoromonomer (b). The fluorine-containing monomer (a) is a monomer having a fluoroalkyl group having 1 to 6 carbon atoms, and the non-fluorine monomer (b) is an acyclic hydrocarbon group and/or nitrogen, oxygen or It is a monomer having a cyclic hydrocarbon group which may contain a sulfur atom. The non-fluorine monomer (b) is preferably a non-fluorine non-crosslinkable monomer having a non-cyclic hydrocarbon group having 14 or more carbon atoms and/or a cyclic hydrocarbon group. The hydrocarbon group of the non-fluorine monomer (b) is saturated or unsaturated, preferably saturated. The fluoropolymer may optionally have repeating units derived from a monomer (c) other than the fluoromonomer (a) and the non-fluoromonomer (b).

The fluorine-containing monomer (a) has the formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. ]
is a compound represented by

X is, for example, a hydrogen atom, a methyl group, a halogen, a linear or branched alkyl group having 2 to 21 carbon atoms, a CFX ¹ X ² group (provided that X ¹ and X ² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. be.
In the fluoropolymer, X is preferably a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. More preferably, X is a hydrogen atom or a methyl group, particularly a methyl group.

Y is preferably -O-.

Z is, for example, a direct bond, a straight-chain alkylene group having 1 to 20 carbon atoms or a branched alkylene group [for example, the formula -(CH ₂ ) _x - (wherein x is 1 to 10.) A group represented by the formula], or a group represented by the formula —SO ₂ N(R ¹ )R ² — or —CON(R ¹ )R ² — (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms and R ² is a straight or branched alkylene group having 1 to 10 carbon atoms.) or the formula —CH ₂ CH(OR ³ )CH ₂ — (wherein R ³ is , a hydrogen atom, or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl)), or a group represented by the formula —Ar—(CH ₂ ) _r — (wherein Ar is a substituted an arylene group optionally having a group, and r is 0 to 10.), or -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or -(CH ₂ ) _m - S—(CH ₂ ) _n — group (where m is 1-10 and n is 0-10).
In the fluoropolymer, Z is preferably a direct bond, an alkylene group having 1 to 20 carbon atoms, or -SO ₂ N(R ¹ )R ² -.

Rf is preferably a perfluoroalkyl group, but may be a fluoroalkyl group having a hydrogen atom. Rf preferably has 4 to 6 carbon atoms, such as 4 or 6 carbon atoms. It is particularly preferred that Rf has 6 carbon atoms. Examples of Rf are _{-CF2CF2CF2CF3 , -CF2CF ( CF3} ) _{2 ,} -C _{( CF3} ) _{3 ,} -(CF2) _5CF3 , -( _CF2 ) _3CF ( _CF3 ) ₂ .

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, the following.
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O- _{C6H4 -} Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 )2N _{( -CH3} )SO2 _- Rf
_CH2 =C(-H)-C ₍ =O)-O-( _CH2 )2N _{( -C2H5} )SO2 _- Rf
_CH2 =C(-H)-C(=O)-O-CH2CH(-OH) _{CH2 -} Rf
_CH2 =C(-H)-C(=O)-O-CH2CH( _-OCOCH3 ) _{CH2 -} Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-H)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-H)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O- _{C6H4 -} Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 )2N _{( -CH3} )SO2 _- Rf
_CH2 =C( _-CH3 )-C ₍ =O)-O-( _CH2 )2N _{( -C2H5} )SO2 _- Rf
_CH2 =C( _-CH3 )-C(=O)-O-CH2CH(-OH) _{CH2 -} Rf
_CH2 =C( _-CH3 )-C(=O)-O-CH2CH( _-OCOCH3 ) _{CH2 -} Rf

_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CH3 )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-F)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-Cl)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF3 )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CF2H)-C(=O)-NH-( _CH2 ) _{2 -} Rf

_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -SO2 _- Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₂ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CN)-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -S-Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -S-( _CH2 ) ₂ -Rf
_CH2 = _{C ( -CF2CF3} )-C(=O)-O-( _CH2 ) ₂ -SO2-Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) _{2 -} SO2-( _CH2 ) ₂ -Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-NH-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-F)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-F)-C(=O)-NH-( _CH2 ) ₃ -Rf

_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-Cl)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CF3 )-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C( _-CF2H )-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -S-Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -S-( _CH2 ) ₂ -Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -SO2 _- Rf
_CH2 =C(-CN)-C(=O)-O-( _CH2 ) ₃ -SO2-( _CH2 ) _{2 -} Rf
_CH2 =C( _-CF2CF3 )-C(=O)-O-( _CH2 ) _{3 -} S-Rf
_CH2 =C( _-CF2CF3 )-C(=O)-O-( _CH2 ) _{3 -} S-( _CH2 ) ₂ -Rf
_CH2 = _{C (-CF2CF3)-C(=O)-O-(CH2)3 - SO2 -} Rf
_CH2 =C _{( -CF2CF3} )-C(=O)-O-( _CH2 ) _{2 -} SO2-( _CH2 ) ₂ -Rf
Of these, _CH2 =CH-C(=O)-O-( _CH2 ) ₂ -Rf, _CH2 =C( _-CH3 )-C(=O)-O-( _CH2 ) ₂ -Rf is preferred.

Non-fluorine monomer (b) is a non-fluorine monomer having a hydrocarbon group.
Non-fluorinated monomers have the formula:
_CH2 = ^CA11 -C(=O) ^-OA12
[In the formula, A ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a is a halogen atom,
A ¹² is a hydrocarbon group having 1 to 40 carbon atoms. ]
It is preferably a (meth)acrylate ester monomer represented by.

The hydrocarbon group may have 1 to 40 carbon atoms, preferably 4 to 40 carbon atoms, especially 14 to 40 carbon atoms.
Examples of hydrocarbon groups are linear or branched saturated or unsaturated (eg, ethylenically unsaturated) aliphatic hydrocarbon groups having 1 to 40 carbon atoms, preferably 14 to 40 carbon atoms, , preferably 6 to 40, such as 14 to 40 saturated or unsaturated (e.g., ethylenically unsaturated) cycloaliphatic groups, 6 to 40, preferably 14 to 40 carbon atoms aromatic hydrocarbon groups, It is an araliphatic hydrocarbon group of 7 to 40, preferably 14 to 40.
The hydrocarbon group is preferably an acyclic hydrocarbon group having 14 to 40 carbon atoms or a cyclic hydrocarbon group having 4 to 40 carbon atoms.

Specific examples of (meth)acrylate ester monomers are
As a (meth)acrylate ester monomer having an acyclic hydrocarbon group,
cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate;
As a (meth)acrylate ester monomer having a cyclic hydrocarbon-containing group,
Cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate.
Stearyl (meth)acrylate and behenyl (meth)acrylate are preferred.

The fluoropolymer is a (meth)acrylate ester monomer represented by the above formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹² , wherein A ¹² is an acyclic hydrocarbon group having 1 to 13 carbon atoms. It is preferred not to have repeat units derived from.

The fluoropolymer optionally has repeating units derived from a monomer (c) other than the monomers (a) and (b).
In one embodiment, the other monomer (c) has the formula:
_CH2 =CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
T is a hydrogen atom, a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom), or a hydrocarbon group having 1 to 40 carbon atoms (eg, 5 to 20). ]
It may be a compound represented by

Other monomers (c) may be, for example, halogenated olefinic monomers.
Halogenated olefin monomers do not have fluorine atoms.
Halogenated olefin monomers may be olefins having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin monomer is preferably an olefin having 2 to 5 carbon atoms and having 2 to 20 carbon atoms, particularly 1 to 5 chlorine atoms. Preferred examples of halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride is preferred because it increases the water and oil repellency (especially the durability of the water and oil repellency). The fluorine-containing polymer preferably does not have repeating units derived from vinylidene chloride.

In another aspect, the other monomer (c) is preferably a non-fluorine crosslinkable monomer containing no fluorine atoms. Non-fluorine crosslinkable monomers may be fluorine-free compounds having at least one reactive group and/or an olefinic carbon-carbon double bond (preferably a (meth)acrylate group). The non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds (preferably (meth)acrylate groups), or at least one olefinic carbon-carbon double bond and at least one It may be a compound having a reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, glycidyl groups, and the like.
By having a reactive group such as a hydroxyl group, it is possible to impart durability to antifouling properties and water and oil repellency.

Non-fluorine crosslinkable monomers may be mono(meth)acrylates, di(meth)acrylates or mono(meth)acrylamides with reactive groups. Alternatively, the non-fluorine crosslinkable monomer may be a di(meth)acrylate.

Examples of non-fluorine crosslinkable monomers are vinyl monomers having hydroxyl groups (especially (meth)acrylate monomers).
Specific examples of non-fluorine crosslinkable monomers include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate. ) acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate be.

Non-fluorine crosslinkable monomers may be isocyanatoacrylate monomers, and the like.
Specific examples of isocyanatoacrylate monomers are 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, 2-isocyanatoethyl (meth)acrylate. 2-butanone oxime adduct of 2-isocyanatoethyl (meth)acrylate pyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3,5-dimethylpyrazole adduct, 2-isocyanatoethyl (meth)acrylate 3-methylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate ε-caprolactam adduct, 3-isocyanatopropyl (meth)acrylate 2-butanone oxime adduct, 3-isocyanatopropyl (meth)acrylate pyrazole adduct, 3-isocyanatopropyl (meth)acrylate 3,5-dimethylpyrazole adduct, 3-isocyanatopropyl (meth)acrylate 3-methylpyrazole adduct, 3-isocyanatopropyl (meth)acrylate ε-caprolactam adduct of 4-isocyanatobutyl (meth)acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth)acrylate pyrazole adduct, 4-isocyanatobutyl (meth)acrylate 3, 5-dimethylpyrazole adduct, 4-isocyanatobutyl (meth)acrylate-3-methylpyrazole adduct, 4-isocyanatobutyl (meth)acrylate-ε-caprolactam adduct, and the like.

The fluorine-containing polymer preferably does not have a polyoxyalkylene group (the number of oxyalkylene groups in the polyoxyalkylene group is 2 or more). For example, the non-fluorine monomer (b) and the other monomer (c) preferably have no polyoxyalkylene group. Thereby, the fluoropolymer can impart good antifouling properties.

As used herein, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

Each of the monomers (a) to (c) may be used alone or in combination of two or more.
The fluorine-containing polymer may be used alone or in combination of two or more.

The amount of the fluoromonomer (a) may be 20-98% by weight, for example 30-90% by weight, especially 40-80% by weight, relative to the fluoropolymer.
The weight ratio of monomer (a) to monomer (b) may be 20:80 to 80:20, 30:70 to 70:30, eg 35:60 to 65:35.

In the fluoropolymer containing the monomer (c), the weight ratio of the monomer (a) to the monomer (b) to the monomer (c) is 20:75:5 to 80:5:15. , preferably 30:65:5 to 70:15:15, for example 40:53:7 to 65:25:10. Alternatively, the amount of the monomer (c) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 100 parts by weight in total of the monomers (a) and (b). may be from 5 to 15, such as from 7 to 12 parts by weight.

The molecular weight of the fluoropolymer may be generally 1,000 to 1,000,000, particularly 2,000 to 50,000, for example, when converted to polystyrene by GPC (gel permeation chromatography) measurement.

A fluorine-containing polymer can be produced by polymerization by a known method using a polymerization initiator, a solvent, and, if necessary, a chain transfer agent. The fluoropolymer can be produced by solution polymerization in an organic solvent, emulsion polymerization in water, or the like.
The paint modifier is preferably a fluoropolymer solution in an organic solvent.

(2) Paint A paint comprises a resin (ie, paint resin). Resins are thermosets or thermoplastics, and are generally thermosets. Examples of resins are urethane resins, epoxy resins, fluorine resins, and melamine resins.

Epoxy resins are compounds having two or more oxirane rings (epoxy groups) in the molecule. Generally, it is used in combination with a curing agent (amine-based curing agent, acid or acid anhydride-based curing agent, basic active hydrogen compound, active hydrogen compound such as imidazoles) as a two-part curing coating. A catalyst may also be added to control the curing reaction rate.

Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, bisphenol A type novolak type epoxy resin, phenol novolak type epoxy resin, ortho cresol novolak type epoxy resin, dicyclopentadiene phenol type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol Ethane type epoxy resin, tetrafunctional type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glyoxal type epoxy resin , alicyclic epoxy resins, alicyclic polyfunctional epoxy compounds, and heterocyclic epoxy resins such as triglycidyl isocyanate (TGIC).

Examples of amine curing agents include aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine; alicyclic polyamines such as isophoronediamine and 1,3-bisaminomethylcyclohexane; aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone. secondary or tertiary amines such as linear diamine, tetramethylguanidine, triethanolamine, piperidine, pyridine, and benzyldimethylamine; obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine; polyamidoamine.

Examples of acid or acid anhydride curing agents include polycarboxylic acids such as adipic acid, azelaic acid, trimellitic acid, pyromellitic acid, decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride; ,3′,4,4′-Benzophenonetetracarboxylic anhydride and other aromatic anhydrides; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and other cycloaliphatic anhydrides; polyadipine Aliphatic anhydrides such as acid anhydrides, polyazelaic anhydride, polysebacic anhydride, dodecenyl succinic anhydride, and poly(ethyl)octadecanedioic anhydride.

Examples of basic active hydrogen compounds are organic acid dihydrazides.

Examples of imidazoles are 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptanedecylimidazole.

Examples of catalysts are tertiary amines, imidazoles, boron trifluoride-amine complexes, organic acid compounds, phenols, organometallic compounds.

A urethane resin is formed from a compound (polyol) having two or more hydroxyl groups and a curing agent which is a compound (isocyanate compound) having two or more isocyanate groups. A urethane resin can be used as a two-component curable paint.

In addition to hydroxyl groups, isocyanate compounds undergo curing reactions with active hydrogen compounds having functional groups such as amino groups, mercapto groups, and carboxyl groups. Therefore, it is possible to adjust the strength of the cured coating film and the stability of the coating by using the polyol in combination with these active hydrogen compounds, or by introducing these active hydrogen functional groups into the polyol molecule.

A catalyst may be added to control the curing reaction rate. By masking the isocyanate groups in advance with a blocking agent, the isocyanate compound can coexist with the polyol in the paint, and can be used as a one-part curable paint that can be heat-cured during the formation of the coating film.

Furthermore, by increasing the molecular weight of the isocyanate compound, the curing reaction can be slowed down, and a so-called moisture-curable coating can be obtained in which the coating is cured by reacting with moisture in the atmosphere.

Examples of polyols are polyhydric alcohols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polypropylene glycol, polytetramethylene Glycols, condensed polyester polyols, lactone polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols, phosphorus-containing polyols, castor oil polyols, hydrogenated castor oil polyols, and phenolic polyols. Preferred polyols are addition polymers with propylene glycol, condensation polyester polyols, lactone polyester polyols, acrylic polyols, polycarbonate polyols and phenol polyols. Polyols may be used in combination of two or more, if necessary.

An isocyanate compound is a compound having two isocyanate groups in one molecule. Examples of isocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) and trimethylhexamethylene diisocyanate (TMDI); alicyclic diisocyanates such as isophorone diisocyanate (IPDI); aromatic diisocyanates such as xylylene diisocyanate (XDI); - Aliphatic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate (TDI) and 4,4-diphenylmethane diisocyanate (MDI); dimer acid diisocyanate (DDI), hydrogenated TDI (HTDI), hydrogenated XDI (H6XDI), Hydrogenated diisocyanates such as hydrogenated MDI (H12MDI); dimers, trimers, tetramers or higher polyisocyanates thereof; polyhydric alcohols such as trimethylolpropane, water or low molecular weight It is an adduct with polyester resin.

A polyol and an isocyanate compound have a short pot life because the urethane curing reaction starts when they are mixed. In order to prolong the pot life, a blocked isocyanate compound obtained by blocking the reactive group (isocyanate group) of the isocyanate compound with a suitable blocking agent can also be used.

Examples of blocking agents include oxime blocking agents such as methyl ethyl ketoxime, acetoxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; phenolic blocking agents such as m-cresol and xylenol; methanol, ethanol, butanol, 2-ethylhexanol, and cyclo. alcohol blocking agents such as hexanol and ethylene glycol monoethyl ether; lactam blocking agents such as ε-caprolactam; diketone blocking agents such as diethyl malonate and acetoacetate; mercaptan blocking agents such as thiophenol; urea-based blocking agents; imidazole-based blocking agents; and carbamic acid-based blocking agents.

Examples of catalysts are tertiary amines, organometallic compounds and carboxylic acid salts of tertiary amines. Examples of tertiary amines are triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethylhexane-1,6-diamine, N,N,N',N'',N''-pentamethyl diethylenetriamine, bis(2-dimethylaminoethyl)ether, 1,2-dimethylimidazole, N-methyl-N'-(2-dimethylamino)ethylpiperazine, diazabicycloundecene. Examples of organometallic compounds are stannus octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltinmercaptide, dibutyltinthiocarboxylate, dibutyltindimaleate, dioctyltinmercaptide, dioctyltinthiocarboxylate, phenylmercuric propionate. acid salt, lead octenoate. Examples of carboxylic acid salts of tertiary amines are the carboxylic acid salts of the above tertiary amines.

Examples of fluoroplastics are homopolymers or copolymers of tetrafluoroethylene, trifluoromonochloroethylene or vinylidene difluoride.

Examples of melamine resins are partially or fully methylolated melamine resins obtained by reaction of melamine with aldehydes. Examples of aldehydes are formaldehyde, paraformaldehyde. In addition, it is also possible to use a methylolated melamine resin in which the methylol groups are partially or completely etherified with an alcohol. Examples of alcohols used for etherification are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol.

In general, paints contain organic solvents in addition to resins. Furthermore, the paint preferably comprises at least one of pigments and auxiliaries.
Examples of pigments are colored pigments (titanium oxide, carbon black, indigo, quinacridone, pearl mica), antirust pigments, metallic pigments (eg titanium oxide, carbon black, indigo, quinacridone, pearl mica).
Examples of auxiliaries are dispersants, desiccants, plasticizers, defoamers, antioxidants (e.g. hindered phenols), UV absorbers (e.g. benzotriazole, benzophenone), rheology control agents (e.g. hydroxyethylcellulose, urea compounds, microgels), curing accelerators (eg, tin compounds, zinc compounds, amine compounds).
Examples of organic solvents are hydrocarbons, alcohols, esters, ketones, cellosolves.

The paint may be used alone or in combination of two or more.

As the paint, for example, a commercially available paint can also be used. For example, urethane paints include Cera M Retan, Cera M Retan Elastic, Ceratect U Mild Top Coat, Arethretan (manufactured by Kansai Paint Co., Ltd.), Hypon 50 Fine, Hypon 50 Top Coat (manufactured by Nippon Paint Co., Ltd.), V Top H Top Coat, V Top HB. Final coating (manufactured by Dainippon Toryo Co., Ltd.), NY Porin (manufactured by Shinto Toryo Co., Ltd.), and the like. Epoxy paints include Esco, Esco NB, Epomarine GX (manufactured by Kansai Paint Co., Ltd.), Hypon 90 Fine, Hypon 90 Moistak (manufactured by Nippon Paint Co., Ltd.), Eponix #20 topcoat, Eponix #3100AP (manufactured by Dainippon Toryo Co., Ltd.), Neogo. -Se-#2300 (manufactured by Shinto Paint Co., Ltd.) and the like. The paint is not limited to the commercially available products listed here, and may be newly synthesized and used, and any paint can be used.

(3) Paint Composition The paint composition comprises a paint modifier (1) containing a fluoropolymer and a paint (2) containing a resin.
The amount of the fluoropolymer may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the resin. The amount of fluoropolymer may be 0.01 to 10% by weight based on the coating composition.
The coating composition can be prepared by mixing a resin-containing coating and a coating modifier. For example, a coating composition can be produced by adding a coating modifier containing a fluoropolymer and an organic solvent to a coating containing a resin and an organic solvent. The organic solvent in the paint may be the same as or different from the organic solvent in the paint modifier.
The coating composition is applied to a substrate such as a metal (eg, steel plate) and the organic solvent is volatilized (eg, at room temperature or outdoor temperature) to form a resin coating.

Although details will be described below with reference to examples, the present disclosure is not limited only to these examples.
In the examples, parts, percentages and ratios refer to parts by weight, weight percentages and weight ratios unless otherwise stated.
Physical properties were measured as follows.

Static Contact Angle Contact angle measurements (at room temperature (25° C.) and droplets of 2 μl) were performed with water, n-hexadecane and ethanol.

Antifouling property The antifouling properties of soil, salt, and algae were evaluated as follows.

For soil and salt, 50% and 3.5% aqueous solutions (i.e., 50% soil suspension and 3.5% salt aqueous solution) were applied, respectively. asked.
Evaluation Criteria ◯: When the coated plate is tilted by 10 degrees, the dirt is quickly removed.
◯△: The stain does not come off even when the coated plate is tilted at 10 degrees, but the stain comes off when it is tilted at 45 degrees.
Δ: Dirt does not come off even when the coated plate is tilted at an angle of 45 degrees, but comes off when struck from the back of the steel plate.
x: Even if the coated plate is tilted at an angle of 45 degrees and even if it is struck from the back side of the steel plate, the dirt does not come off.

For algae, a coated steel plate was placed in a tank in which goldfish were bred for 3 months, and the degree of adhesion of algae was determined.
Evaluation Criteria ◯: Algae do not adhere to the surface of the coating film.
Δ: Algae adheres to the surface of the coating film, but is peeled off when the steel plate is lifted from the water surface.
x: Algae adhered to the coating film surface and did not come off even when the steel plate was lifted from the water surface.

A static friction coefficient and a dynamic friction coefficient were measured using a friction coefficient surface property measuring machine and steel balls as friction elements in accordance with ASTM D1894.

The surface of the scratch-resistant coating film is rubbed back and forth 10 times at a speed of 100 mm/min under a load of 100 gf using Scotch Brite (manufactured by 3M). Thereafter, Ra (arithmetic average roughness) and Rzjis (ten-point average roughness) were measured on the coating film surface at a measurement distance of 40 mm using a surface roughness meter. Those with low values were judged to be less likely to be scratched.

Polymer Examples 1-16
A solution of a fluorine-containing copolymer was produced by mixing the monomers shown in Table 1 (fluorine-containing monomers and non-fluorine-containing monomers) with 100 parts by weight of isopropyl alcohol (IPA) and polymerizing the mixture. Then, the organic solvent (IPA) was removed by distillation to obtain a bulk fluorine-containing copolymer. The monomer composition in the fluorine-containing copolymer was almost the same as the composition of the charged monomers.
Table 1 shows the monomers used in Polymer Examples 1-16.

The meanings of abbreviations in Table 1 are as follows.
C6FA: _CH2 =C ₍ -H)-C(=O)-O-( _CH2 ) _{2 -} C6F13
C6FMA: _CH2 =C _{( -CH3} )-C(=O)-O-( _CH2 ) _{2 -} C6F13
C6FCLA: _CH2 =C ₍ -Cl)-C(=O)-O-( _CH2 ) _{2 -} C6F13
LA: Lauryl acrylate StA: Stearyl acrylate VA: Behenyl acrylate CHMA: Cyclohexyl methacrylate EOA-1: CH ₂ =C(-H)-C(=O)-O-(CH ₂ CH ₂ O)n- H.
Average of n number 4.5
EOA-2: CH ₂ =C(-H)-C(=O)-O-(CH ₂ CH ₂ O)n-H
Average of n number 8
2-HEA: 2-hydroxyethyl acrylate 2-HEMA: 2-hydroxyethyl methacrylate VDC: vinylidene chloride

Example 1
A solution obtained by mixing 0.6 parts by weight of the fluorine-containing copolymer obtained in Polymer Example 1 and 2.4 parts by weight of methyl ethyl ketone (MEK) was added to 20 parts by weight of Eponix #10 topcoat curing agent (manufactured by Dainippon Toryo Co., Ltd.). and stirred. After that, it was mixed with 80 parts by weight of Eponix #10 top coating main agent (manufactured by Dainippon Toryo Co., Ltd.) to obtain a coating composition containing an epoxy coating. This coating composition was applied to a steel plate and dried overnight to obtain a coating film.
Tables 2 and 5 show the composition of the coating composition and the test results.

Example 2
A solution obtained by mixing 0.3 parts by weight of the fluorine-containing copolymer obtained in Polymer Example 2 and 1.2 parts by weight of MEK was mixed with 20 parts by weight of Eponix #10 topcoat curing agent (manufactured by Dainippon Toryo Co., Ltd.). A coating film was obtained in the same manner as in Example 1 except that the mixture was stirred.
Table 2 shows the composition of the coating composition and the test results.

Example 3
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 2 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 4
A coating film was obtained in the same manner as in Example 2, except that 1.8 parts by weight of the fluorine-containing copolymer and 7.2 parts by weight of MEK were used.
Table 2 shows the composition of the coating composition and the test results.

Example 5
A coating film was obtained in the same manner as in Example 2, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 6
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 7
A coating film was obtained in the same manner as in Example 4, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 8
A coating film was obtained in the same manner as in Example 2, except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 9
A coating film was obtained in the same manner as in Example 4, except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 10
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 5 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 11
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 6 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 12
A coating film was obtained in the same manner as in Example 2, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 13
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 14
A coating film was obtained in the same manner as in Example 4, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 15
A coating film was obtained in the same manner as in Example 2, except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 16
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 17
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 9 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 18
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 10 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 19
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 11 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 20
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 12 was used.
Table 2 shows the composition of the coating composition and the test results.

Example 21
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 13 was used.
Table 2 shows the composition of the coating composition and the test results.

Comparative example 1
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 14 was used.
Table 2 shows the composition of the coating composition and the test results.

Comparative example 2
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 15 was used.
Table 2 shows the composition of the coating composition and the test results.

Comparative example 3
A coating film was obtained in the same manner as in Example 1, except that the fluorine-containing copolymer obtained in Polymer Example 16 was used.
Table 2 shows the composition of the coating composition and the test results.

Comparative example 4
A coating composition was obtained by mixing 20 parts by weight of Eponix #10 topcoat curing agent (manufactured by Dainippon Toryo Co., Ltd.) and 80 parts by weight of Eponix #10 topcoat main agent (manufactured by Dainippon Toryo Co., Ltd.). This coating composition was applied to a steel plate and dried overnight to obtain a coating film. The solid content of this paint after drying was 61%.
Tables 2 and 5 show the composition of the coating composition and the test results.

Example 31
A solution obtained by mixing 0.57 parts by weight of the fluorine-containing copolymer obtained in Polymer Example 1 and 2.4 parts by weight of MEK was mixed with 20 parts by weight of an areretane curing agent (manufactured by Kansai Paint Co., Ltd.) and stirred. After that, it was mixed with 80 parts by weight of Arrestane (white) base (manufactured by Kansai Paint Co., Ltd.) to obtain a coating composition containing a urethane resin. This coating composition was applied to a steel plate and dried overnight to obtain a coating film.
Tables 3 and 4 show the composition of the coating composition and the test results.

Example 32
A coating film was obtained in the same manner as in Example 1, except that a mixed solution of 0.29 parts by weight of the fluorine-containing copolymer obtained in Polymer Example 2 and 1.2 parts by weight of MEK was used.
Tables 3 and 4 show the composition of the coating composition and the test results.

Example 33
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 2 was used.
Tables 3 and 4 show the composition of the coating composition and the test results.

Example 34
A coating film was obtained in the same manner as in Example 32, except that 1.71 parts by weight of the fluorine-containing copolymer and 7.2 parts by weight of MEK were used.
Tables 3 and 4 show the composition of the coating composition and the test results.

Example 35
A coating film was obtained in the same manner as in Example 32, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 36
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 37
A coating film was obtained in the same manner as in Example 34, except that the fluorine-containing copolymer obtained in Polymer Example 3 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 38
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 4 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 39
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 5 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 40
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 6 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 41
A coating film was obtained in the same manner as in Example 32, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 42
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 43
A coating film was obtained in the same manner as in Example 34, except that the fluorine-containing copolymer obtained in Polymer Example 7 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 44
A coating film was obtained in the same manner as in Example 32, except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 45
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 8 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 46
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 9 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 47
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 10 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 48
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 11 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 49
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 12 was used.
Table 3 shows the composition of the coating composition and the test results.

Example 50
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 13 was used.
Table 3 shows the composition of the coating composition and the test results.

Comparative example 11
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 14 was used.
Table 3 shows the composition of the coating composition and the test results.

Comparative example 12
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 15 was used.
Table 3 shows the composition of the coating composition and the test results.

Comparative example 3
A coating film was obtained in the same manner as in Example 31, except that the fluorine-containing copolymer obtained in Polymer Example 16 was used.
Table 3 shows the composition of the coating composition and the test results.

Comparative example 14
A paint composition was obtained by mixing 20 parts by weight of an arethrethane curing agent (manufactured by Kansai Paint Co., Ltd.) and 80 parts by weight of an arethrethane (white) base (manufactured by Kansai Paint Co., Ltd.). This coating composition was applied to a steel plate and dried overnight to obtain a coating film. The solid content of this paint after drying was 57%.
Tables 3 and 4 show the composition of the coating composition and the test results.

The coating composition can be used for buildings such as bridges and houses (eg, harbor structures, exterior walls of houses, building materials), machines (eg, exteriors of mechanical equipment, machine tools), vehicles, and ships. Examples of substrates to which the coating composition is applied are metal (especially steel such as steel plate), concrete, wood.

Claims (14)

(a) Formula:
_CH2 =C(-X)-C(=O)-YZ-Rf
[Wherein, X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. ]
and a repeating unit derived from a fluorine-containing monomer represented by the formula (b):
_CH2 = ^CA11 -C(=O) ^-OA12
[In the formula, A ¹¹ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or a is a halogen atom,
A ¹² is a hydrocarbon group having 1 to 40 carbon atoms. ]
A paint modifier comprising a fluorine-containing polymer having a repeating unit derived from a non-fluorine monomer which is a (meth)acrylate ester monomer represented by: In the fluorine-containing monomer (a),
X is a hydrogen atom, a methyl group or a chlorine atom,
Z is a direct bond, a linear or branched alkylene group having 1 to 20 carbon atoms,
2. The paint modifier according to claim 1, wherein Rf is a perfluoroalkyl group having 4 to 6 carbon atoms. 3. The paint modifier according to claim 1, wherein in the fluorine-containing monomer (a), X is a methyl group. In the non-fluorine monomer (b), A ¹¹ is a hydrogen atom or a methyl group, and A ¹² is an acyclic hydrocarbon group having 14 to 40 carbon atoms or a cyclic hydrocarbon group having 4 to 40 carbon atoms. The paint modifier according to any one of claims 1 to 3. The amount of the fluoromonomer (a) is 20 to 98% by weight relative to the fluoropolymer, and the weight ratio of the monomer (a) to the monomer (b) is 20:80 to 80. : 20, the paint modifier according to any one of claims 1 to 4. The fluorine-containing copolymer further contains a repeating unit formed from a non-fluorine crosslinkable monomer or another monomer (c) that is a non-fluorine crosslinkable monomer,
The non-fluorine crosslinkable monomer has the formula:
_CH2 =CA-T
[In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
T is a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 40 carbon atoms. ]
is a compound represented by
the non-fluorine crosslinkable monomer is a compound having at least two olefinic carbon-carbon double bonds, or at least one olefinic carbon-carbon double bond and at least one reactive group;
6. The method according to any one of claims 1 to 5, wherein the amount of monomer (c) is 1 to 30 parts by weight with respect to a total of 100 parts by weight of monomers (a) and (b). Paint modifier. The fluoropolymer is composed of a (meth)acrylate ester monomer represented by the formula: CH ₂ =CA ¹¹ -C(=O)-OA ¹² , wherein A ¹² is an acyclic hydrocarbon group having 1 to 13 carbon atoms. It does not have one or both of repeating units derived from repeating units and repeating units derived from vinylidene chloride, or the fluorine-containing polymer contains a polyoxyalkylene group (the number of oxyalkylene groups in the polyoxyalkylene group is 2 or more .), the paint modifier according to any one of claims 1 to 6. The paint modifier according to any one of claims 1 to 7, which is an organic solvent solution of a fluoropolymer. (1) A paint modifier comprising the fluorine-containing polymer according to any one of claims 1 to 8; and (2) a paint composition comprising a paint comprising a resin. 10. The coating composition according to claim 9, wherein the resin is at least one selected from the group consisting of urethane resins, epoxy resins, fluorine resins and melamine resins. The coating composition according to claim 9 or 10, wherein the amount of the fluorine-containing polymer is 0.1 to 20 parts by weight per 100 parts by weight of the resin. A method for producing the coating composition according to any one of claims 9 to 11,
A production method comprising polymerizing the monomer (a) and the monomer (b) to obtain a fluoropolymer, and then mixing the fluoropolymer with a paint. A method of coating a substrate, comprising applying the coating composition according to any one of claims 9 to 11 to the surface of a substrate to form a coating film, and imparting antifouling properties to the substrate. A coating composition film formed by applying the coating composition according to any one of claims 9 to 11 to the surface of a substrate.