Modified polymer, composition, coating film, and laminate

Abstract

To provide a modified polymer having excellent antifouling properties.SOLUTION: The disclosure relates to a modified polymer including (a) a main chain containing a fluorinated polymer and (b) a side chain represented by the following formula (b1') and / or (b2'). The formula (b1') is -CH2-CRb1(-X)-C(=O)-Y-Z-Rf, wherein X is a hydrogen atom, a methyl group, or a halogen atom; Y is -O- or -NH-; Z is a direct bond or a divalent organic group; Rf is a C1-C20 fluoroalkyl group; and Rb1 is a hydrogen atom or a monovalent organic group. The formula (b2') is -CH2-CRb2(-R1)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2]n-O-Si(-CH3)2-R2, wherein R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or a methyl group; Rb2 is a hydrogen atom or a monovalent organic group; and n is 3 to 200.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a modified polymer, a composition, a coating film, and a laminate.

Background Art

[0002] Fluorine-containing polymers are excellent in weather resistance and the like because of the high bond energy and low polarizability of the C-F bonds in the molecule. However, in applications such as building materials, excellent antifouling properties in addition to weather resistance and the like are required, and various studies have been conducted.

[0003] For example, Patent Document 1 discloses a composition containing (A) a synthetic resin containing a functional group X, (B) an antifouling component, and (C) a curing agent, wherein the antifouling component (B) is a liquid polydialkylsiloxane having (B1) a functional group X and Z or a functional group Y capable of reacting with the curing agent (C), 1 or (B2) a liquid fluoropolyether having a functional group X and Z or a functional group Y capable of reacting with the curing agent (C). 2 A coating composition is described.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present disclosure aims to provide a modified polymer having excellent antifouling properties.

Means for Solving the Problems

[0006] The present disclosure provides a modified polymer (hereinafter also referred to as "the first modified polymer of the present disclosure") having (a) a main chain composed of a fluorine-containing polymer and (b) a side chain represented by formula (b1') and / or formula (b2'). -CH2-CR b1 (-X)-C(=O)-Y-Z-Rf (b1’) [Wherein, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and R b1 is a hydrogen atom or a monovalent organic group.] -CH2-CR b2 (-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2’) [Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, R b2 is a hydrogen atom or a monovalent organic group, and n is 3 to 200.]

[0007] The present disclosure also provides a modified polymer (hereinafter also referred to as "the second modified polymer of the present disclosure") obtained by reacting (a) a fluorine-containing polymer and (b) a monomer represented by formula (b1) and / or formula (b2) in an organic solvent in the presence of a radical polymerization initiator, characterized by having a main chain composed of the fluorine-containing polymer and side chains based on the monomer. CH2=C(-X)-C(=O)-Y-Z-Rf (b1) [Wherein, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] CH2=C(-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2) [Wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, and n is 3 to 200.] Hereinafter, when simply described as "the modified polymer of the present disclosure" without any particular disclaimer, it means a concept including both the first modified polymer and the second modified polymer of the present disclosure above.

[0008] The fluorine-containing polymer preferably has a unit represented by -CHR- (wherein R is a hydrogen atom or a monovalent organic group).

[0009] The fluorine-containing polymer preferably contains a polymerization unit based on tetrafluoroethylene or chlorotrifluoroethylene.

[0010] The present disclosure also provides a composition containing the above modified polymer.

[0011] The composition of the present disclosure preferably further contains a solvent.

[0012] The composition of the present disclosure preferably further contains a curing agent.

[0013] The composition of the present disclosure is preferably a paint.

[0014] The composition of the present disclosure is preferably an anti-freezing and / or anti-frosting composition.

[0015] The present disclosure further provides a coating film obtained by applying the above composition.

[0016] The coating film of the present disclosure preferably has a water contact angle of 95° or more and a gloss retention rate of 80% or more after 3000 hours of QUVB.

[0017] The coating film of the present disclosure preferably has a water contact angle of 80° or more after 1000 hours of QUVB and an oil contact angle of 25° or more after 1000 hours of QUVB.

[0018] The present disclosure also provides a laminate including a substrate and the above coating film.

Advantages of the Invention

[0019] The modified polymer of the present disclosure has the above-described configuration, and thus has excellent antifouling properties.

Mode for Carrying Out the Invention

[0020] Hereinafter, the modified polymer of the present disclosure will be specifically described.

[0021] Conventionally, as in Patent Document 1, a method of adding an antifouling component to a synthetic resin to improve antifouling properties has been carried out, but the improvement of antifouling properties has not been sufficient. The modified polymer of the present disclosure has been found and completed by having a main chain composed of a fluorine-containing polymer and a specific side chain, whereby excellent antifouling properties can be imparted to the fluorine-containing polymer. Hereinafter, the modified polymer of the present disclosure will be described in more detail.

[0022] The first modified polymer of the present disclosure has a main chain (a) composed of a fluorine-containing polymer. The fluorine-containing polymer is known as a resin having excellent heat resistance, chemical resistance, weather resistance, etc. The modified polymer of the present disclosure has obtained excellent antifouling properties by having a specific side chain (b) in addition to the excellent heat resistance, chemical resistance, weather resistance, etc. that the fluorine-containing polymer originally has.

[0023] The above fluorine-containing polymer preferably has a unit represented by -CHR- (wherein R is a hydrogen atom or a monovalent organic group). The -CHR- bond may be contained at least one in the main chain. Further, it is also preferable that the above fluorine-containing polymer contains a polymerization unit of -CH2-CHR-.

[0024] In the unit represented by -CHR-, R is a hydrogen atom or a monovalent organic group.

[0025] Examples of the above monovalent organic group include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, A heteroaryl group which may have one or more substituents, A cyano group, A formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2-, and, RaNRbSO2- (In these formulas, Ra is independently, An alkyl group which may have one or more substituents, An alkenyl group which may have one or more substituents, An alkynyl group which may have one or more substituents, A cycloalkyl group which may have one or more substituents, A cycloalkenyl group which may have one or more substituents, A cycloalkadienyl group which may have one or more substituents, An aryl group which may have one or more substituents, An aralkyl group which may have one or more substituents, A non-aromatic heterocyclic group which may have one or more substituents, or A heteroaryl group which may have one or more substituents, Rb is independently H or an alkyl group which may have one or more substituents.) Is included. As the above organic group, an alkyl group which may have one or more substituents is preferable.

[0026] Also, in this specification, "substituent" means a group that can be substituted. Examples of the "substituent" include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, an aliphatic sulfonamide group, an aromatic sulfonamide group, a heterocyclic sulfonamide group, an amino group, an aliphatic amino group, an aromatic amino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic sulfinyl group, an aromatic sulfinyl group, an aliphatic thio group, an aromatic thio group, a hydroxy group, a cyano group, a sulfo group, a carboxy group, an aliphatic oxyamino group, an aromatic oxyamino group, a carbamoylamino group, a sulfamoylamino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a di-aliphatic oxyphosphinyl group, and a di-aromatic oxyphosphinyl group.

[0027] The above aliphatic group may be saturated or unsaturated, and may also have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aliphatic group include an alkyl group having 1 to 8 carbon atoms in total, preferably 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a vinyl group, a cyclohexyl group, a carbamoylmethyl group, etc.

[0028] The above aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aromatic group include an aryl group having 6 to 12 carbon atoms, preferably 6 to 10 total carbon atoms, such as a phenyl group, a 4-nitrophenyl group, a 4-acetylaminophenyl group, a 4-methanesulfonylphenyl group, etc.

[0029] The above heterocyclic group may have a halogen atom, a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above heterocyclic group include a 5- to 6-membered heterocycle having 2 to 12 total carbon atoms, preferably 2 to 10, such as a 2-tetrahydrofuryl group, a 2-pyrimidyl group, etc.

[0030] The above acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxy group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above acyl group include an acyl group having 2 to 8 total carbon atoms, preferably 2 to 4, such as an acetyl group, a propanoyl group, a benzoyl group, a 3-pyridinecarbonyl group, etc.

[0031] The above acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. Examples of the above acylamino group include an acylamino group having 2 to 12 total carbon atoms, preferably 2 to 8, and an alkylcarbonylamino group having 2 to 8 total carbon atoms, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0032] The above aliphatic oxycarbonyl group may be saturated or unsaturated, and may also have a hydroxy group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aliphatic oxycarbonyl group include an alkoxycarbonyl group having 2 to 8 carbon atoms in total, preferably 2 to 4 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, (t)-butoxycarbonyl group, etc.

[0033] The above carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. Examples of the above carbamoyl group include an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 2 to 5 carbon atoms in total, such as N-methylcarbamoyl group, N,N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.

[0034] The above aliphatic sulfonyl group may be saturated or unsaturated, and may also have a hydroxy group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aliphatic sulfonyl group include an alkylsulfonyl group having 1 to 6 carbon atoms in total, preferably 1 to 4 carbon atoms in total, such as methanesulfonyl, etc.

[0035] The above aromatic sulfonyl group may have a hydroxy group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, etc. Examples of the above aromatic sulfonyl group include an arylsulfonyl group having 6 to 10 carbon atoms in total, such as benzenesulfonyl, etc.

[0036] The above amino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc.

[0037] The acylamino group may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc. The acylamino group may be an acylamino group having 2 to 12 carbon atoms in total, preferably 2 to 8 carbon atoms in total, more preferably an alkylcarbonylamino group having 2 to 8 carbon atoms in total, such as an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propanoylamino group, etc.

[0038] The aliphatic sulfonamide group, aromatic sulfonamide group, and heterocyclic sulfonamide group may be, for example, a methanesulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group, etc.

[0039] The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, etc. The sulfamoyl group may be a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, a dialkylsulfamoyl group having 2 to 10 carbon atoms in total, an arylsulfamoyl group having 7 to 13 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a dialkylsulfamoyl group having 3 to 6 carbon atoms in total, an arylsulfamoyl group having 6 to 11 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 10 carbon atoms in total, such as a sulfamoyl group, a methylsulfamoyl group, an N,N-dimethylsulfamoyl group, a phenylsulfamoyl group, a 4-pyridinesulfamoyl group, etc.

[0040] The aliphatic oxy group may be saturated or unsaturated and may have a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc. The aliphatic oxy group may be an alkoxy group having 1 to 8 carbon atoms in total, preferably 1 to 6 carbon atoms in total, such as a methoxy group, an ethoxy group, an i-propyloxy group, a cyclohexyloxy group, a methoxyethoxy group, etc.

[0041] The above aromatic amino group and heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group condensed with the aryl group, an aliphatic oxycarbonyl group, preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a carbamoyl group having 1 to 4 carbon atoms in total, a nitro group, and an aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total.

[0042] The above aliphatic thio group may be saturated or unsaturated, and examples thereof include an alkylthio group having 1 to 8 carbon atoms in total, more preferably an alkylthio group having 1 to 6 carbon atoms in total, such as a methylthio group, an ethylthio group, a carbamoylmethylthio group, a t-butylthio group, and the like.

[0043] The above carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group, etc. Examples of the above carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 10 carbon atoms in total, an arylcarbamoylamino group having 7 to 13 carbon atoms in total, a heterocyclic carbamoylamino group having 3 to 12 carbon atoms in total, preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 carbon atoms in total, a dialkylcarbamoylamino group having 3 to 6 carbon atoms in total, an arylcarbamoylamino group having 7 to 11 carbon atoms in total, a heterocyclic carbamoylamino group having 3 to 10 carbon atoms in total, for example, a carbamoylamino group, a methylcarbamoylamino group, an N,N-dimethylcarbamoylamino group, a phenylcarbamoylamino, a 4-pyridinecarbamoylamino group, and the like.

[0044] R is preferably a functional group-containing group. Examples of the functional group include a hydroxyl group (excluding the hydroxyl group contained in the carboxyl group; the same shall apply hereinafter), a carboxyl group, an ester bond (-OCO-), a group represented by -COOCO-, a cyano group, an amino group, an epoxy group, a silyl group, and the like. Among them, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, a group represented by -COOCO-, an amino group, a cyano group, and a silyl group is preferable, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, an amino group, and a silyl group is more preferable, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester bond, and an amino group is still more preferable, and at least one group selected from the group consisting of a hydroxyl group, an ester bond, and a carboxyl group is particularly preferable. Specifically, as the above R, a carboxyl group, -O p -R d q -OH (wherein R d is a linear or branched alkylene group having 1 to 10 carbon atoms, p is 0 or 1, and q is 0 or 1.), -OCO-R e (wherein R e is a hydrocarbon group having 1 to 10 carbon atoms), and the like can be mentioned. The above R e may be a linear or branched hydrocarbon group (for example, an alkyl group, etc.) or a cyclic hydrocarbon group (for example, a cycloalkyl group, a phenyl group, etc.). Preferably, the above R is a group containing a curable functional group. Examples of the curable functional group include a hydroxyl group, a carboxyl group, a group represented by -COOCO-, a cyano group, an amino group, an epoxy group, a silyl group, etc. Among them, from the viewpoint of good curing reactivity, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by -COOCO-, an amino group, a cyano group, and a silyl group is preferable, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a silyl group is more preferable, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group is still more preferable, and at least one group selected from the group consisting of a hydroxyl group and a carboxyl group is particularly preferable. These curable functional groups are usually introduced into the fluoropolymer by copolymerizing a monomer containing a curable functional group.

[0045] Since the above fluoropolymer is excellent in weather resistance, it is preferably a fluoropolymer containing a curable functional group. Examples of the fluoropolymer containing a curable functional group include a polymer obtained by introducing a curable functional group into a fluoropolymer. By having the above configuration, weather resistance and antifouling properties can be made compatible at a more excellent level. Note that the fluoropolymer containing a curable functional group includes a resinous polymer having a clear melting point, an elastomeric polymer exhibiting rubber elasticity, and a thermoplastic elastomeric polymer in between.

[0046] Since the above fluoropolymer is excellent in weather resistance and is also easily soluble in an ester-based solvent, it preferably contains a fluoromonomer unit, a vinyl ester unit containing neither a hydroxyl group nor an aromatic ring, and a monomer unit containing a hydroxyl group. By having the above configuration, weather resistance and antifouling properties can be made compatible at a more excellent level.

[0047] Examples of the fluorine-containing monomer that constitutes the fluorine-containing monomer unit include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, fluorovinyl ether, etc., and one or more of these can be used.

[0048] Among these, the fluorine-containing monomer is preferably at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride, and more preferably at least one selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene, because it has excellent weather resistance. By having the above configuration, weather resistance and antifouling properties can be made compatible at a more excellent level.

[0049] As the vinyl ester that constitutes the vinyl ester unit, vinyl carboxylate is preferable, and at least one selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexanecarboxylate is more preferable, and at least one selected from the group consisting of vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexanecarboxylate is even more preferable, and at least one selected from the group consisting of vinyl acetate and vinyl versatate is particularly preferable.

[0050] In addition, as the vinyl ester, vinyl carboxylate having 6 or more carbon atoms in the carboxylic acid is preferable, and vinyl carboxylate having 9 or more carbon atoms in the carboxylic acid is more preferable because it is further excellent in adhesion and abrasion resistance. The upper limit of the number of carbon atoms in the carboxylic acid in the vinyl carboxylate is preferably 20, and more preferably 15. Vinyl versatates such as vinyl neodecanoate and vinyl neodecanoate are most preferable because they have excellent adhesion to the substrate.

[0051] The above vinyl ester contains neither a hydroxyl group nor an aromatic ring. Further, it is preferable that the above vinyl ester does not contain a halogen atom.

[0052] Examples of the hydroxyl group-containing monomer that constitutes the above hydroxyl group-containing monomer unit include at least one selected from the group consisting of hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxycarboxylic acid vinyl ester, hydroxycarboxylic acid allyl ester, and hydroxyalkyl (meth)acrylate. At least one selected from the group consisting of hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether is more preferable, and hydroxyalkyl vinyl ether is even more preferable.

[0053] Examples of the above hydroxyalkyl vinyl ether include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, and the like.

[0054] Examples of the above hydroxyalkyl allyl ether include 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.

[0055] Examples of the above hydroxycarboxylic acid vinyl ester include vinyl hydroxyacetate, vinyl hydroxypropionate, vinyl hydroxybutyrate, vinyl hydroxyhexanoate, and vinyl 4-hydroxycyclohexylacetate.

[0056] Examples of the above hydroxycarboxylic acid allyl ester include allyl hydroxyacetate, allyl hydroxypropionate, allyl hydroxybutyrate, allyl hydroxyhexanoate, and allyl 4-hydroxycyclohexylacetate.

[0057] Examples of the above hydroxyalkyl (meth)acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like.

[0058] Among the above hydroxyl group-containing monomers, Formula (A): CH2=CH-(CH2) l -O-(CH2) m -OH (In the formula, l is 0 or 1, and m is an integer from 2 to 20) are more preferable, and at least one monomer selected from the group consisting of 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, and 4-hydroxybutyl allyl ether is particularly preferable.

[0059] The content of the above fluorine-containing monomer unit is preferably 30 to 60 mol%, more preferably 40 to 55 mol%, based on all the monomer units of the fluorine-containing polymer.

[0060] The content of the vinyl ester unit containing neither the above hydroxyl group nor the aromatic ring is preferably 1 to 40 mol%, more preferably 10 to 30 mol%, based on all the monomer units of the fluorine-containing polymer.

[0061] The content of the above hydroxyl group-containing monomer unit is preferably 15 to 40 mol%, more preferably 20 to 35 mol%, based on all the monomer units of the fluorine-containing polymer.

[0062] In this specification, the content of each of the above monomer units constituting the fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis according to the type of monomer.

[0063] The fluorine-containing polymer preferably has a number average molecular weight of 3,000 to 100,000. The number average molecular weight is more preferably 5,000 or more, still more preferably 8,000 or more, more preferably 50,000 or less, and still more preferably 35,000 or less. If the number average molecular weight is too small, the weather resistance, solvent resistance and stain resistance will be poor, and at the same time, it may not be possible to form a coating film with high hardness. If the number average molecular weight is too large, the viscosity of the paint may increase and it may be difficult to handle. The number average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

[0064] The fluorine-containing polymer preferably has a glass transition temperature (second run) determined by a differential scanning calorimeter (DSC) of 10 to 70 °C, more preferably 15 to 60 °C. If the glass transition temperature is too small, the weather resistance, solvent resistance and stain resistance will be poor, and at the same time, it may not be possible to form a coating film with high hardness. If the glass transition temperature is too large, the viscosity of the paint may increase and it may be difficult to handle.

[0065] The fluorine-containing polymer preferably has an acid value of 0.6 to 50 mgKOH / g, more preferably 2 to 30 mgKOH / g, from the viewpoint of good compatibility with polyisocyanate compounds, pigments, etc.

[0066] The above fluorine-containing polymer may further contain a monomer unit different from the fluorine-containing monomer unit, the vinyl ester unit containing neither the above hydroxyl group nor the aromatic ring, and the hydroxyl group-containing monomer unit. For example, the above fluorine-containing polymer may contain units such as vinyl carboxylate containing an aromatic ring and no hydroxyl group, carboxyl group-containing monomer, amino group-containing monomer, hydrolyzable silyl group-containing monomer, alkyl vinyl ether containing no hydroxyl group, olefin containing no halogen atom and hydroxyl group, etc. The content of these monomer units may be 0 to 10 mol%, preferably 0.1 to 5 mol%, more preferably 0.5 to 3 mol% based on all the monomer units of the above fluorine-containing polymer.

[0067] Examples of the above vinyl carboxylate containing an aromatic ring and no hydroxyl group include vinyl benzoate, vinyl p-t-butylbenzoate, etc.

[0068] Examples of the above carboxyl group-containing monomer include Formula (B): R 1a R 2a C=CR 3a -(CH2) n -COOH (In the formula, R 1a , R 2a and R 3a are the same or different and are each a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms; n is an integer of 0 or more), and those represented are preferred. For example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, 22-tricosenoic acid, etc. may be mentioned. Among them, at least one selected from the group consisting of acrylic acid, crotonic acid and undecenoic acid is preferred, and at least one selected from the group consisting of acrylic acid and crotonic acid is more preferred.

[0069] Examples of the carboxyl group-containing monomer also include cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitate, citraconic acid, mesaconic acid, aconitic acid, etc.

[0070] Examples of the amino group-containing monomer include, for example, aminovinyl ethers represented by CH2=CH-O-(CH2) x -NH2 (x = 0 to 10); amines represented by CH2=CH-O-CO(CH2) x -NH2 (x = 1 to 10); and others such as aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide, etc.

[0071] Examples of the hydrolyzable silyl group-containing monomer include (meth)acrylic acid esters such as CH2=CHCO2(CH2)3Si(OCH3)3, CH2=CHCO2(CH2)3Si(OC2H5)3, CH2=C(CH3)CO2(CH2)3Si(OCH3)3, CH2=C(CH3)CO2(CH2)3Si(OC2H5)3, CH2=CHCO2(CH2)3SiCH3(OC2H5)2, CH2=C(CH3)CO2(CH2)3SiC2H5(OCH3)2, CH2=C(CH3)CO2(CH2)3Si(CH3)2(OC2H5), CH2=C(CH3)CO2(CH2)3Si(CH3)2OH, CH2=CH(CH2)3Si(OCOCH3)3, CH2=C(CH3)CO2(CH2)3SiC2H5(OCOCH3)2, CH2=C(CH3)CO2(CH2)3SiCH3(N(CH3)COCH3)2, CH2=CHCO2(CH2)3SiCH3〔ON(CH3)C2H5〕2, CH2=C(CH3)CO2(CH2)3SiC6H5〔ON(CH3)C2H5〕2; vinyl silanes such as CH2=CHSi[ON=C(CH3)(C2H5)]3, CH2=CHSi(OCH3)3, CH2=CHSi(OC2H5)3, CH2=CHSiCH3(OCH3)2, CH2=CHSi(OCOCH3)3, CH2=CHSi(CH3)2(OC2H5), CH2=CHSi(CH3)2SiCH3(OCH3)2, CH2=CHSiC2H5(OCOCH3)2, CH2=CHSiCH3〔ON(CH3)C2H5〕2, vinyl trichlorosilane or partial hydrolyzates thereof; vinyl ethers such as trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, etc.

[0072] Examples of the above alkyl vinyl ether without a hydroxyl group include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, octadecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, etc. Among them, at least one selected from the group consisting of ethyl vinyl ether and cyclohexyl vinyl ether is preferable.

[0073] Examples of the above olefin include non-fluorinated olefins such as ethylene, propylene, n-butene, and isobutene.

[0074] The above fluorine-containing polymer preferably has a hydroxyl value of 50 mgKOH / g or more. As the above hydroxyl value, 55 mgKOH / g or more is more preferable, 60 mgKOH / g or more is more preferable, 80 mgKOH / g or more is still more preferable, 100 mgKOH / g or more is particularly preferable, and 180 mgKOH / g or less is preferable, 170 mgKOH / g or less is more preferable, 160 mgKOH / g or less is still more preferable, 150 mgKOH / g or less is particularly preferable.

[0075] The above hydroxyl value is determined by calculation from the weight of the above fluorine-containing polymer and the number of moles of -OH groups. The number of moles of -OH groups can be determined by NMR measurement, IR measurement, titration, elemental analysis, etc.

[0076] The above fluorine-containing polymer can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a bulk polymerization method. Among them, those obtained by the solution polymerization method are preferable.

[0077] The above fluorine-containing polymer is preferably produced by polymerizing a monomer that gives the above unit by a solution polymerization method using an organic solvent and a polymerization initiator. The polymerization temperature is usually 0 to 150°C, preferably 5 to 95°C. The polymerization pressure is usually 0.1 to 10 MPaG (1 to 100 kgf / cm 2 G).

[0078] Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirit; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide; or mixtures thereof.

[0079] Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate (and reducing agents such as sodium bisulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline can be used in combination as necessary); redox initiators composed of an oxidizing agent (e.g., ammonium peroxide, potassium peroxide, etc.), a reducing agent (e.g., sodium sulfite, etc.), and a transition metal salt (e.g., iron sulfate, etc.); diacyl peroxides such as acetyl peroxide and benzoyl peroxide; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxy esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate; and azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis[2-(hydroxymethyl)propionitrile], and 4,4'-azobis(4-cyanopentenoic acid) can be used.

[0080] The first modified polymer of the present disclosure has a side chain (b) represented by the following formula (b1') and / or formula (b2'). -CH2-CR b1 (-X)-C(=O)-Y-Z-Rf (b1') [In the formula, X is a hydrogen atom, a methyl group, or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, R b1is a hydrogen atom or a monovalent organic group. -CH2-CR b2 (-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2’) [In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, R b2 is a hydrogen atom or a monovalent organic group, n is 3 to 200. By having the above specific side chain (b), excellent antifouling properties can be imparted to the fluorine-containing polymer.

[0081] In formula (b1’), X is a hydrogen atom, a methyl group or a halogen atom. X may be a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0082] Y is preferably -O-.

[0083] Z is, for example, a direct bond, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly an alkylene group), for example, a group represented by the formula -(CH2) x -(wherein x is 1 to 10), or a group represented by the formula -R 2 (R 1 )N-SO2- or a group represented by the formula -R 2 (R 1 )N-CO- (wherein R 1 is an alkyl group having 1 to 10 carbon atoms, and R 2 is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms).), or a group represented by the formula -CH2CH(OR 3 )CH2-(Ar-O) p -(wherein R 3is a hydrogen atom, or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl, etc.), Ar is an arylene group optionally having a substituent, and p represents 0 or 1.), or a group represented by the formula -CH2-Ar-(O) q -(wherein Ar is an arylene group optionally having a substituent, and q is 0 or 1.), -(CH2) m -SO2-(CH2) n -group or -(CH2) m -S-(CH2) n -group (provided that m is 1 to 10 and n is 0 to 10). Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cycloaliphatic group having 6 to 18 carbon atoms, -CH2CH2N(R 1 )SO2-group (provided that R 1 is an alkyl group having 1 to 4 carbon atoms.), -CH2CH(OZ 1 )CH2-(Ph-O) p -group (provided that Z 1 is a hydrogen atom or an acetyl group, Ph is a phenylene group, and p is 0 or 1.), -(CH2) n -Ph-O-group (provided that Ph is a phenylene group and n is 0 to 10.), -(CH2) m -SO2-(CH2) n -group or -(CH2) m -S-(CH2) n -group (provided that m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, for example, 1 or 2). The aromatic group or the cycloaliphatic group may be substituted or unsubstituted. The S group or the SO2 group may be directly bonded to the Rf group.

[0084] The Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is 1 to 20, preferably 1 to 6, more preferably 4 to 6, and particularly 6. Although a fluorine-containing monomer having 1 to 20 carbon atoms in the Rf group may be used, the fluorine-containing monomer preferably consists only of compounds in which the Rf group has 4 to 6 carbon atoms, particularly 6. Examples of the Rf group include -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(CF2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8F 17 and the like.

[0085] R b1 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. The monovalent organic group may be represented by the following formula (b1”) or formula (b2”). -CH2-CH(-X)-C(=O)-Y-Z-Rf (b1”) [In the formula, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ] -CH2-CH(-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2”) [In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, and n is 3 to 200. ]

[0086] Specific examples of the side chain represented by the formula (b1’) include, for example, the following, but are not limited thereto. -CH2-CH2-C(=O)-O-(CH2)2-Rf -CH2-CH2-C(=O)-O-C6H4-Rf -CH2-CH2-C(=O)-O-(CH2)2N(-CH3)SO2-Rf -CH2-CH2-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf -CH2-CH2-C(=O)-O-CH2CH(-OH)CH2-Rf

[0087] -CH2-CH2-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf -CH2-CH2-C(=O)-O-(CH2)2-S-Rf -CH2-CH2-C(=O)-O-(CH2)2-S-(CH2)2-Rf -CH2-CH2-C(=O)-O-(CH2)3-SO2-Rf -CH2-CH2-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf -CH2-CH2-C(=O)-NH-(CH2)2-Rf [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0088] Next, the side chain represented by the formula (b2’) will be described.

[0089] In the above formula (b2’), R 1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

[0090] In the above formula (b2’), the above R 2 is a hydrogen atom or a methyl group, preferably a methyl group. In the above formula (b2’), the above R b2 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. Further, the monovalent organic group may be represented by the following formula (b1”) or formula (b2”). -CH2-CH(-X)-C(=O)-Y-Z-Rf (b1”) [wherein, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] -CH2-CH(-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2”) [wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, n is 3 to 200.]

[0091] The above n is 3 to 200. The above n is preferably 5 to 200, more preferably 9 to 200. The side chain represented by the above formula (b2’) may have a low molecular weight or a high molecular weight. From the viewpoint of compatibility, a low molecular weight is preferred. When it has a low molecular weight, n is preferably 3 to 100, more preferably 5 to 80, still more preferably 9 to 70. From the viewpoint of water and oil repellency, a high molecular weight is preferred. When it has a high molecular weight, n is preferably 100 to 200, more preferably 120 to 200, still more preferably 140 to 200.

[0092] Specific examples of the above formula (b2’) include, but are not limited to, the following. -CH2-CH2-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-H -CH2-CH2-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-CH3 -CH2-CH(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-H -CH2-CH(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-CH3 [In the above formula, n is from 3 to 200.]

[0093] The weight average molecular weight of the above side chain (b) is preferably 300 or more. More preferably, it is 400 or more, still more preferably 600 or more, and particularly preferably 800 or more. Also, the molecular weight of the above side chain (b) is preferably 20000 or less, more preferably 15000 or less, and still more preferably 10000 or less.

[0094] The first modified polymer of the present disclosure may be any one in which the above side chain (b) is bonded to the carbon atom of the fluorine-containing polymer constituting the main chain (a). For example, it is preferably one in which one of the hydrogen atoms bonded to the carbon atom of the fluorine-containing polymer constituting the main chain (a) is substituted with the side chain (b). The first modified polymer of the present disclosure, for example, has -CHR a - or -CRR a - units (wherein R a represents the side chain (b). R is the same as above.) in the main chain (a).

[0095] In the first modified polymer of the present disclosure, R of the side chain represented by the formula (b1') b1 and R of the side chain represented by the formula (b2') b2 may be a monovalent organic group R c based on the non-fluorine crosslinkable monomer (c).

[0096] The above non-fluorine crosslinkable monomer (c) is preferably a non-fluorine crosslinkable (meth)acrylate or (meth)acrylamide monomer. The non-fluorine crosslinkable monomer (c) is preferably a (meth)acrylate or (meth)acrylamide having a reactive group. The reactive group is preferably an active hydrogen-containing group or an active hydrogen-reactive group, such as a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a ketone group, a hydrazide group, and a melamine group. The non-fluorine crosslinkable monomer (c) is preferably an active hydrogen-containing monomer (for example, a monomer having a hydroxyl group, an amino group, a carboxyl group, a ketone group, a hydrazide group, and / or a melamine group) or an active hydrogen-reactive group-containing monomer (for example, a monomer having an epoxy group, a chloromethyl group, a blocked isocyanate group, a carboxyl group, and / or a hydrazide group), and more preferably an active hydrogen-containing monomer. A particularly preferred reactive group is a hydroxyl group.

[0097] A monovalent organic group R based on a (meth)acrylate or (meth)acrylamide having a reactive group c is represented by the formula: -CH2-CHX 1 -C(=O)-Y 1 -Z 1 -W [wherein X 1 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), Y 1 is -O- or -NH-, Z 1 is a direct bond or a divalent organic group, W is a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a ketone group, a hydrazide group, or a melamine group. ] is preferably a group represented by.

[0098] A monovalent organic group R based on a (meth)acrylate or (meth)acrylamide having a hydroxyl group c is represented by the formula: -CH2-CHX 1 -C(=O)-Y 1 -Z 1-OH [wherein, X 1 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), Y 1 is -O- or -NH-, Z 1 is a direct bond or a divalent organic group.] A group represented by is particularly preferable. Z 1 is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly, an alkylene group), for example, a group represented by the formula -(CH2) x -(wherein x is 1 to 10). Examples of the non-fluorine crosslinkable monomer (c) include N-methylol(meth)acrylamide, N-2-proparol(meth)acrylamide, N-butylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxybutyl(meth)acrylate, diacetone(meth)acrylamide, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-acetoxyacetoxyethyl(meth)acrylate, glycidyl(meth)acrylate, and the like.

[0099] As the non-fluorine crosslinkable monomer (c), a hydroxyl group-containing monomer is preferable from the viewpoint of increasing the crosslinking density and enhancing the coating film strength. Examples of the hydroxyl group-containing monomer include hydroxyethyl(meth)acrylate and hydroxybutyl(meth)acrylate.

[0100] As the non-fluorine crosslinkable monomer (c), an epoxy group-containing monomer is preferable from the viewpoint of improving the compatibility with a solvent or the like. Examples of the epoxy group-containing monomer include glycidyl(meth)acrylate.

[0101] The first modified polymer of the present disclosure may be one in which the monovalent organic group R c is bonded to a carbon atom of the fluorine-containing polymer constituting the main chain (a), and one of the hydrogen atoms bonded to the carbon atom of the fluorine-containing polymer constituting the main chain (a) is the monovalent organic group Rc It may be replaced with The first modified polymer of the present disclosure, for example, has -CHR c - or -CRR c - units represented by (wherein R c and R are the same as described above).) It may have

[0102] For the first modified polymer of the present disclosure, it is preferable that the mass ratio of the main chain (a) to the side chain (b) (main chain (a) / side chain (b)) is 50 / 1 to 50 / 50. The mass ratio (main chain (a) / side chain (b)) is more preferably 50 / 1 to 50 / 30, and even more preferably 50 / 1 to 50 / 10.

[0103] For the first modified polymer of the present disclosure, it is preferable that the mass ratio of the main chain (a) to the side chain (c) (main chain (a) / side chain (c)) is 50 / 1 to 50 / 50. The mass ratio (main chain (a) / side chain (b)) is more preferably 50 / 1 to 50 / 30, and even more preferably 50 / 1 to 50 / 10.

[0104] For the first modified polymer of the present disclosure, it is preferable that the number of side chains (b) is 1 to 10 with respect to one main chain (a). More preferably, it is 8 or less, and even more preferably 5 or less.

[0105] For the first modified polymer of the present disclosure, it is preferable that the number average molecular weight is 300 to 15000. The number average molecular weight is more preferably 400 or more, even more preferably 800 or more, more preferably 12000 or less, and even more preferably 9000 or less. If the number average molecular weight is too small, there is a possibility that a coating film having high hardness cannot be formed while being excellent in weather resistance, solvent resistance, and stain resistance. If the number average molecular weight is too large, the viscosity when used as a paint may increase and handling may become difficult. The number average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.

[0106] The first modified polymer of the present disclosure can be produced in the same manner as the second modified polymer of the present disclosure described below. Therefore, the matters described in the second modified polymer of the present disclosure described below can also be adopted in the first modified polymer of the present disclosure. Further, the matters described in the first modified polymer of the present disclosure can also be adopted in the second modified polymer of the present disclosure.

[0107] The second modified polymer of the present disclosure is obtained by reacting (a) a fluorine-containing polymer and (b) a monomer represented by formula (b1) and / or formula (b2) in an organic solvent in the presence of a radical polymerization initiator, and has a main chain based on the fluorine-containing polymer (a) and side chains based on the monomer (b) represented by formula (b1) and / or formula (b2). CH2=C(-X)-C(=O)-Y-Z-Rf (b1) [In the formula, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ] CH2=C(-R 1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2) [In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, n is 3 to 200. ]

[0108] The above-mentioned fluorine-containing polymer is the same as the fluorine-containing polymer described in the first modified polymer of the present disclosure.

[0109] The monomer (b1) represented by the above formula (b1) has the formula: CH2=C(-X)-C(=O)-Y-Z-Rf (b1) [In the formula, X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.] It is a compound represented by the following formula.

[0110] In the above formula (b1), X, Y, Z and Rf are the same as X, Y, Z and Rf in the aforementioned formula (b1'), and the preferred embodiments can also be adopted in the same manner.

[0111] Specific examples of the above monomer-(b1) include, for example, the following, but are not limited thereto. CH2=C(-H)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-C6H4-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

[0112] 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 [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0113] The monomer-(b2) represented by the above formula (b2) has the formula: CH2=C(-R1 )-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-R 2 (b2) [wherein, R 1 is a hydrogen atom or a methyl group, R 2 is a hydrogen atom or a methyl group, and n is from 3 to 200.] It is a monomer represented by

[0114] R in the above formula (b2) 1 , R 2 and n are the same as R 1 , R 2 and n in the aforementioned formula (b2’), and the preferred embodiments can also be adopted in the same manner.

[0115] Specific examples of the monomer-(b2) represented by the above formula (b2) include, for example, the following, but are not limited thereto. CH2=C(-H)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-H CH2=C(-H)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-CH3 CH2=C(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-H CH2=C(-CH3)-C(=O)-O-Si(-CH3)2-[O-Si(-CH3)2] n -O-Si(-CH3)2-CH3 [In the above formula, n is from 3 to 200.]

[0116] The weight average molecular weight of the above monomer-(b) is preferably 300 or more. More preferably 400 or more, still more preferably 600 or more, and particularly preferably 800 or more. Also, the molecular weight of the above monomer-(b) is preferably 20000 or less, more preferably 15000 or less, and still more preferably 10000 or less.

[0117] It is also preferable that the second modified polymer of the present disclosure is obtained by further reacting a non-fluorine crosslinkable monomer (c). The non-fluorine crosslinkable monomer (c) is the same as those exemplified in the first modified polymer of the present disclosure.

[0118] For example, as the non-fluorine crosslinkable monomer (c), (meth)acrylate or (meth)acrylamide having a reactive group has the formula: CH2=CX 1 -C(=O)-Y 1 -Z 1 -W [wherein X 1 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), Y 1 is -O- or -NH-, Z 1 is a direct bond or a divalent organic group, W is a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a ketone group, a hydrazide group, or a melamine group.] It is preferably a compound represented by.

[0119] Also, as the non-fluorine crosslinkable monomer (c), (meth)acrylate or (meth)acrylamide having a hydroxyl group has the formula: CH2=CX 1 -C(=O)-Y 1 -Z 1 -OH [wherein X 1 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), Y 1 is -O- or -NH-, Z 1 is a direct bond or a divalent organic group.] It is particularly preferably a compound represented by. Z 1is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly, an alkylene group), for example, a group represented by the formula -(CH2) x -(wherein x is 1 to 10). Examples of the non-fluorine crosslinkable monomer (c) include N-methylol (meth)acrylamide, N-2-proparol (meth)acrylamide, N-butylol (meth)acrylamide, hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, diacetone (meth)acrylamide, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoxyacetoxyethyl (meth)acrylate, glycidyl (meth)acrylate and the like.

[0120] As described above, by reacting the fluorine-containing polymer and the monomer in an organic solvent in the presence of a radical polymerization initiator, a modified polymer having a main chain composed of the fluorine-containing polymer and side chains based on the monomer can be obtained. By the above reaction, side chains to which one or two or more monomers are bonded are obtained. Those in which two or more monomers are bonded may also be used. The number of bonds of the monomer is preferably 3 or less, more preferably 2 or less.

[0121] The temperature of the above reaction is particularly preferably 60°C or higher, more preferably 70°C or higher, and still more preferably 80°C or higher. Also, it is preferably 150°C or lower, more preferably 140°C or lower, and still more preferably 135°C or lower.

[0122] In the above reaction, the amount of the monomer (b) is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer (a).

[0123] In the above reaction, the amount of the monomer (c) is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the fluorine-containing polymer (a).

[0124] In the above reaction, the fluorine-containing polymer may be reacted with monomers (b) and (c) simultaneously, or the fluorine-containing polymer may be reacted with monomer (b) first and then monomer (c) may be further reacted. It is preferable to react the fluorine-containing polymer with monomers (b) and (c) simultaneously.

[0125] Examples of the organic solvent include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, mineral spirit; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, isopropanol, ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, dioxane; dimethyl sulfoxide, or mixtures thereof.

[0126] Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate (and reducing agents such as sodium bisulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline can be used in combination as needed); redox initiators composed of an oxidizing agent (such as ammonium peroxide and potassium peroxide) and a reducing agent (such as sodium sulfite) and a transition metal salt (such as iron sulfate); diacyl peroxides such as acetyl peroxide and benzoyl peroxide [BPO]; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; alkyl peroxy esters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis[2-(hydroxymethyl)propionitrile], and 4,4'-azobis(4-cyanopentenoic acid) can be used.

[0127] The amount of the radical polymerization initiator used is preferably 0.01 to 0.5 parts by mass based on the total amount of the monomers. More preferably, it is 0.05 parts by mass or more, still more preferably, it is 0.1 parts by mass or more, and also more preferably, it is 0.3 parts by mass or less, still more preferably, it is 0.2 parts by mass or less.

[0128] The above reaction is preferably further carried out in the presence of a chain transfer agent. Examples of the chain transfer agent include mercaptan group-containing compounds such as dodecyl mercaptan, lauryl mercaptan, thioglycol, and thioglycerol (particularly, (for example, alkyl mercaptans having 1 to 30 carbon atoms)), inorganic salts such as sodium hypophosphite and sodium bisulfite, and the like. The amount of the chain transfer agent used may be in the range of 0.1 to 50 parts by mass, for example, 2 to 20 parts by mass, based on 100 parts by mass of the total amount of the monomers.

[0129] The above reaction is preferably carried out by stirring a mixture containing a fluorine-containing polymer, monomer(s) (b1) and / or (b2), an organic solvent, and a radical polymerization initiator.

[0130] As a specific method for obtaining the second modified polymer of the present disclosure, for example, a fluorine-containing polymer and an organic solvent are added to a reaction vessel, the temperature is raised to 80 to 90 °C, and stirred as necessary, and then the above monomer(s) (b1) and / or (b2) are added, a chain transfer agent and a radical polymerization initiator are added, and then stirred.

[0131] The modified polymer of the present disclosure has a main chain of a fluorine-containing polymer and side chains having a specific structure, and thus can impart excellent antifouling properties in addition to properties such as weather resistance of the fluorine-containing polymer.

[0132] The present disclosure also provides a composition containing the modified polymer of the present disclosure.

[0133] The composition of the present disclosure preferably further contains a solvent. As the above solvent, water or an organic solvent is preferred. As the above organic solvent, esters such as ethyl acetate, n-butyl acetate, tert-butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; cyclic ethers such as tetrahydrofuran, dioxane; amides such as N,N-dimethylformamide, N,N-dimethylacetamide; aromatic hydrocarbons such as toluene, xylene; alcohols such as propylene glycol methyl ether; hydrocarbons such as hexane, heptane; mixed solvents thereof, etc. can be mentioned. Also, third-class organic solvents under the Industrial Safety and Health Act and solvents corresponding thereto, which are called weak solvents, can be mentioned. When making an organic solvent solution, the concentration of the modified polymer of the present disclosure may be 5 to 95% by mass, preferably 10 to 80% by mass. By containing a solvent as described above, the composition of the present disclosure can be suitably used as a paint.

[0134] The above composition preferably further contains a curing agent. When the above composition contains the curable functional group-containing fluoropolymer as the above fluoropolymer, it is particularly preferable that the above composition contains a curing agent.

[0135] The above curing agent is a compound that reacts with the curable functional group of the curable functional group-containing fluoropolymer and crosslinks. For example, isocyanates, amino resins, acid anhydrides, polyepoxy compounds, isocyanate group-containing silane compounds, etc. are usually used. Among them, isocyanates are preferred.

[0136] Specific examples of the above-mentioned isocyanates include, for example, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts thereof, biuret bodies and isocyanurate bodies, polymers thereof having two or more isocyanate groups, and further blocked isocyanates, etc., but are not limited thereto. Among them, the isocyanurate body is preferred.

[0137] Specific examples of the above-mentioned amino resins include, for example, urea resins, melamine resins, benzoguanamine resins, glycoluril resins, as well as methylolated melamine resins obtained by methylolating melamine, and alkyl etherified melamine resins obtained by etherifying methylolated melamine with alcohols such as methanol, ethanol, and butanol, etc., but are not limited thereto.

[0138] Specific examples of the above-mentioned acid anhydrides include, for example, phthalic anhydride, pyromellitic anhydride, mellitic anhydride, etc., but are not limited thereto.

[0139] As the polyepoxy compound and the isocyanate group-containing silane compound, for example, those described in JP-A-2-232250, JP-A-2-232251, etc. can be used. Preferred examples include, for example,

Chemical formula

[0140] As the above polyisocyanate compound, at least one polyisocyanate compound derived from at least one isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis(isocyanatomethyl)cyclohexane (hydrogenated XDI, H6XDI), a blocked isocyanate compound based on hexamethylene diisocyanate (HDI), a polyisocyanate compound derived from hexamethylene diisocyanate (HDI), a polyisocyanate compound derived from isophorone diisocyanate (IPDI), and a water-dispersible polyisocyanate compound is preferred.

[0141] When using, as the above polyisocyanate compound, a polyisocyanate compound (hereinafter also referred to as polyisocyanate compound (I)) derived from at least one isocyanate (hereinafter also referred to as isocyanate (i)) selected from the group consisting of xylylene diisocyanate (XDI) and bis(isocyanatomethyl)cyclohexane (hydrogenated XDI, H6XDI), the adhesion becomes more excellent.

[0142] Examples of the above polyisocyanate compound (I) include an adduct obtained by addition polymerization of the above isocyanate (i) and an aliphatic polyhydric alcohol having 3 or more valences, an isocyanurate structure (nurate structure) composed of the above isocyanate (i), and a biuret composed of the above isocyanate (i).

[0143] Examples of the above adduct include the following general formula (1):

[0144]

Chemical formula

[0145] (In the formula, R 1 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. R 2 represents a phenylene group or a cyclohexylene group. k is an integer of 3 to 20.) Those having a structure represented by are preferred. R in the general formula (1) above 1 is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and still more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. When the above R 2 is a phenylene group, it may be any of a 1,2-phenylene group (o-phenylene group), a 1,3-phenylene group (m-phenylene group), and a 1,4-phenylene group (p-phenylene group). Among them, a 1,3-phenylene group (m-phenylene group) is preferred. Also, all Rs in the general formula (1) above 2 may be the same phenylene group, or two or more kinds may be mixed. When the above R 2 is a cyclohexylene group, it may be any of a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group. Among them, a 1,3-cyclohexylene group is preferred. Also, all Rs in the general formula (1) above 2 may be the same cyclohexylene group, or two or more kinds may be mixed. The above k is a number corresponding to the valence of the trivalent or higher aliphatic polyhydric alcohol. As the above k, more preferably, it is an integer of 3 to 10, and still more preferably, it is an integer of 3 to 6.

[0146] The above isocyanurate structure has one or more isocyanurate rings represented by the following general formula (2):

[0147]

Chemical formula

[0148] and has one or more isocyanurate rings represented by the following general formula (2): Examples of the above isocyanurate structure include trimers obtained by the trimerization reaction of the above isocyanate, pentamers obtained by the pentamerization reaction, heptamers obtained by the heptamerization reaction, and the like. Among them, the following general formula (3):

[0149] [Chemical formula]

[0150] (In the formula, R 2 is the same as R 2 in general formula (1).) A trimer represented by the formula is preferred. That is, the above isocyanurate structure is preferably a trimer of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis(isocyanatomethyl)cyclohexane.

[0151] The above biuret is represented by the following general formula (4):

[0152] [Chemical formula]

[0153] (In the formula, R 2 is the same as R 2 in general formula (1).) It is a compound having a structure represented by the formula, and can be obtained by trimerizing the above isocyanate under conditions different from those for obtaining the above isocyanurate structure.

[0154] Among the above polyisocyanate compounds (I), in particular, the above adduct, that is, at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis(isocyanatomethyl)cyclohexane, and a trivalent or higher aliphatic polyhydric alcohol are preferably obtained by addition polymerization.

[0155] When the above polyisocyanate compound (I) is an adduct of the above isocyanate (i) and an aliphatic polyhydric alcohol having a valence of 3 or more, specific examples of the aliphatic polyhydric alcohol having a valence of 3 or more include glycerol, trimethylolpropane (TMP), 1,2,6 - hexanetriol, trimethylolethane, 2,4 - dihydroxy - 3 - hydroxymethylpentane, 1,1,1 - tris(bishydroxymethyl)propane, 2,2 - bis(hydroxymethyl)butanol - 3 and other trihydric alcohols; pentaerythritol, diglycerol and other tetrahydric alcohols; arabinitol, ribitol, xylitol and other pentahydric alcohols (pentitols); sorbitol, mannitol, galactitol, allozylositol and other hexahydric alcohols (hexitols) and the like. Among them, trimethylolpropane and pentaerythritol are particularly preferred.

[0156] In addition, examples of the xylylene diisocyanate (XDI) used as a constituent component of the above adduct include 1,3 - xylylene diisocyanate (m - xylylene diisocyanate), 1,2 - xylylene diisocyanate (o - xylylene diisocyanate), 1,4 - xylylene diisocyanate (p - xylylene diisocyanate). Among them, 1,3 - xylylene diisocyanate (m - xylylene diisocyanate) is preferred.

[0157] In addition, examples of bis(isocyanatomethyl)cyclohexane (hydrogenated XDI, H6XDI) used as a constituent component of the above adduct include 1,3 - bis(isocyanatomethyl)cyclohexane, 1,2 - bis(isocyanatomethyl)cyclohexane, 1,4 - bis(isocyanatomethyl)cyclohexane. Among them, 1,3 - bis(isocyanatomethyl)cyclohexane is preferred.

[0158] An adduct can be obtained by addition polymerization of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis(isocyanatomethyl)cyclohexane and the above - mentioned aliphatic polyhydric alcohol having a valence of 3 or more.

[0159] As the above adduct, specifically, for example, the following general formula (5):

[0160]

Chemical formula

[0161] (In the formula, R 3 represents a phenylene group or a cyclohexylene group.) A compound represented by, that is, at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis(isocyanatomethyl)cyclohexane, and trimethylolpropane (TMP), and a polyisocyanate compound obtained by addition polymerization thereof can be mentioned. Regarding the phenylene group or cyclohexylene group represented by R 3 in the above general formula (5), it is as described for R 2 in the above general formula (1).

[0162] Examples of commercially available products of the polyisocyanate compound represented by the above general formula (5) include Takenate D110N (manufactured by Mitsui Chemicals, adduct of XDI and TMP, NCO content 11.8%), Takenate D120N (manufactured by Mitsui Chemicals, adduct of H6XDI and TMP, NCO content 11.0%), etc.

[0163] Specific examples of the case where the above polyisocyanate compound (I) is an isocyanurate structure include Takenate D121N (manufactured by Mitsui Chemicals, H6XDI nurate, NCO content 14.0%), Takenate D127N (manufactured by Mitsui Chemicals, H6XDI nurate, trimer of H6XDI, NCO content 13.5%), etc.

[0164] By using a blocked isocyanate based on hexamethylene diisocyanate (HDI) (hereinafter, also simply referred to as blocked isocyanate) as the above polyisocyanate compound, the above composition will have a sufficient pot life. As the above block isocyanate, those obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter also referred to as polyisocyanate compound (II)) with a blocking agent are preferred. Examples of the above polyisocyanate compound (II) include an adduct obtained by addition polymerization of hexamethylene diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, an isocyanurate structure (nurate structure) composed of hexamethylene diisocyanate, and a biuret composed of hexamethylene diisocyanate.

[0165] Examples of the above adduct include the following general formula (6):

[0166]

Chemical formula

[0167] (In the formula, R 4 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. k is an integer of 3 to 20.) Those having a structure represented by are preferred. R in the above general formula (6) 4 is a hydrocarbon group based on the above aliphatic polyhydric alcohol having a valence of 3 or more, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. The above k is a number corresponding to the valence of the aliphatic polyhydric alcohol having a valence of 3 or more. As the above k, more preferably, it is an integer of 3 to 10, and even more preferably an integer of 3 to 6.

[0168] The above isocyanurate structure has one or more isocyanurate rings represented by the following general formula (2) in the molecule:

[0169]

Chemical formula

[0170] and having two or more. Examples of the above isocyanurate structure include trimers obtained by the trimerization reaction of the above isocyanate, pentamers obtained by the pentamerization reaction, heptamers obtained by the heptamerization reaction, and the like. Among them, the following general formula (7):

[0171]

Chemical formula

[0172] The trimer represented by is preferred.

[0173] The above biuret is a compound having the structure represented by the following general formula (8):

[0174]

Chemical formula

[0175] It can be obtained by trimerizing hexamethylene diisocyanate under conditions different from those for obtaining the above isocyanurate structure.

[0176] As the above blocking agent, it is preferable to use a compound having active hydrogen. As the compound having active hydrogen, for example, it is preferable to use at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds.

[0177] Thus, the above blocked isocyanate is obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate with a blocking agent, and the blocking agent is preferably at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds.

[0178] When the polyisocyanate compound (II) for obtaining the above block isocyanate is an adduct of hexamethylene diisocyanate and an aliphatic polyhydric alcohol having three or more valences, specific examples of the aliphatic polyhydric alcohol having three or more valences include glycerol, trimethylolpropane (TMP), 1,2,6 - hexanetriol, trimethylolethane, 2,4 - dihydroxy - 3 - hydroxymethylpentane, 1,1,1 - tris(bishydroxymethyl)propane, 2,2 - bis(hydroxymethyl)butanol - 3 and other trihydric alcohols; pentaerythritol, diglycerol and other tetrahydric alcohols; arabinitol, ribitol, xylitol and other pentahydric alcohols (pentitols); sorbitol, mannitol, galactitol, allozylositol and other hexahydric alcohols (hexitols), etc. Among them, trimethylolpropane and pentaerythritol are particularly preferred. The above adduct can be obtained by addition polymerization of hexamethylene diisocyanate and an aliphatic polyhydric alcohol having three or more valences as described above.

[0179] Specific examples of the compound having active hydrogen to be reacted with the above polyisocyanate compound (II) include alcohols such as methanol, ethanol, n - propanol, isopropanol, methoxypropanol, etc.; oximes such as acetone oxime, 2 - butanone oxime, cyclohexanone oxime, etc.; lactams such as ε - caprolactam, etc.; active methylene compounds such as methyl acetoacetate, ethyl malonate, etc.; pyrazole compounds such as 3 - methylpyrazole, 3,5 - dimethylpyrazole, 3,5 - diethylpyrazole, etc. One or more of these can be used. Among them, active methylene compounds and oximes are preferred, and active methylene compounds are more preferred.

[0180] Examples of commercially available block isocyanates include Duranate K6000 (manufactured by Asahi Kasei Chemicals Corporation, an active methylene compound block isocyanate of HDI), Duranate TPA - B80E (manufactured by Asahi Kasei Chemicals Corporation), Duranate MF - B60X (manufactured by Asahi Kasei Chemicals Corporation), Duranate 17B - 60PX (manufactured by Asahi Kasei Chemicals Corporation), Coronate 2507 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate 2513 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate 2515 (manufactured by Nippon Polyurethane Industry Co., Ltd.), Sumidule BL - 3175 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Luxate HC1170 (manufactured by Olin Chemicals), Luxate HC2170 (manufactured by Olin Chemicals), and the like.

[0181] As the polyisocyanate compound, a polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter also referred to as polyisocyanate compound (III)) can also be used. Examples of the polyisocyanate compound (III) include those described above as the polyisocyanate compound (II).

[0182] Specific examples of the polyisocyanate compound (III) include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., an isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%), Sumidule N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., an isocyanurate structure of hexamethylene diisocyanate), Takenate D170N (manufactured by Mitsui Chemicals, Inc., an isocyanurate structure of hexamethylene diisocyanate), Sumidule N3800 (manufactured by Sumitomo Bayer Urethane Co., Ltd., an isocyanurate structure prepolymer type of hexamethylene diisocyanate), Desmodule N3390 (manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO content 19.6%), D - 370N (manufactured by Mitsui Chemicals, Inc., NCO content 25.0%), AE - 700 (manufactured by Asahi Kasei Corporation, NCO content 11.9%), D - 201 (manufactured by Mitsui Chemicals, Inc., NCO content 15.8%), and the like.

[0183] As the above polyisocyanate compound, a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter, also referred to as polyisocyanate compound (IV)) can also be used.

[0184] Examples of the above polyisocyanate compound (IV) include an adduct obtained by addition polymerization of isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, an isocyanurate structure (nurate structure) composed of isophorone diisocyanate, and a biuret composed of isophorone diisocyanate.

[0185] Examples of the above adduct include the following general formula (9):

[0186]

Chemical formula

[0187] (In the formula, R 5 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. R 6 is a group represented by the following general formula (10):

[0188]

Chemical formula

[0189] It preferably has a structure represented by). k is an integer of 3 to 20. R in the above general formula (9) 5 is a hydrocarbon group based on the above aliphatic polyhydric alcohol having a valence of 3 or more, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. The above k is a number corresponding to the valence of the aliphatic polyhydric alcohol having a valence of 3 or more. More preferably, k is an integer of 3 to 10, and even more preferably an integer of 3 to 6.

[0190] The above isocyanurate structure has, in the molecule, the following general formula (2):

[0191]

Chem.

[0192] It has one or more isocyanurate rings represented by the following formula. Examples of the above isocyanurate structure include trimers obtained by the trimerization reaction of isophorone diisocyanate, pentamers obtained by the pentamerization reaction, heptamers obtained by the heptamerization reaction, and the like. Among them, the following general formula (11):

[0193]

Chem.

[0194] (In the formula, R 6 is the same as R 6 in the general formula (9).) The trimer represented by the formula is preferred. That is, the above isocyanurate structure is preferably a trimer of isophorone diisocyanate.

[0195] The above biuret is a compound having a structure represented by the following general formula (12):

[0196]

Chem.

[0197] (In the formula, R 6 is the same as R 6 in the general formula (9).) It can be obtained by trimerizing isophorone diisocyanate under conditions different from those for obtaining the above isocyanurate structure.

[0198] Among the above polyisocyanate compounds (IV), it is preferably at least one selected from the group consisting of the above adduct and the above isocyanurate structure. That is, the above polyisocyanate compound (IV) is preferably at least one selected from the group consisting of an adduct obtained by addition polymerization of isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, and an isocyanurate structure composed of isophorone diisocyanate.

[0199] When the above polyisocyanate compound (IV) is an adduct of isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more, specific examples of the aliphatic polyhydric alcohol having a valence of 3 or more include trihydric alcohols such as glycerol, trimethylolpropane (TMP), 1,2,6 - hexanetriol, trimethylolethane, 2,4 - dihydroxy - 3 - hydroxymethylpentane, 1,1,1 - tris(bishydroxymethyl)propane, 2,2 - bis(hydroxymethyl)butanol - 3; tetrahydric alcohols such as pentaerythritol, diglycerol; pentavalent alcohols (pentitols) such as arabitol, ribitol, xylitol; hexavalent alcohols (hexitols) such as sorbitol, mannitol, galactitol, allozylosit, etc. Among them, trimethylolpropane and pentaerythritol are particularly preferred.

[0200] By subjecting isophorone diisocyanate and an aliphatic polyhydric alcohol having a valence of 3 or more as described above to addition polymerization, an adduct suitably used in the present invention can be obtained.

[0201] Specific examples of the adduct preferably used in the present invention include, for example, the following general formula (13):

[0202]

Chemical formula

[0203] (In the formula, R 7 is the following general formula (10):

[0204] [Chemical formula]

[0205] It is a group represented by the following formula. Compounds represented by the formula (i.e., polyisocyanate compounds obtained by the addition polymerization of isophorone diisocyanate and trimethylolpropane (TMP)) can be mentioned.

[0206] Examples of commercially available polyisocyanate compounds represented by the general formula (10) (TMP adduct of isophorone diisocyanate) include Takenate D140N (manufactured by Mitsui Chemicals, NCO content: 11%).

[0207] Examples of commercially available isocyanurate structures composed of isophorone diisocyanate include Desmodur Z4470 (manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO content: 11%).

[0208] As the above polyisocyanate compound, a water-dispersible polyisocyanate compound can also be used. The water-dispersible polyisocyanate compound refers to a polyisocyanate compound that can form an aqueous dispersion when added to an aqueous medium and stirred. Examples of such water-dispersible polyisocyanate compounds include (1) a mixture of a hydrophobic polyisocyanate and a polyisocyanate having a hydrophilic group, (2) a mixture of a hydrophobic polyisocyanate and a dispersant having no isocyanate group but having a hydrophilic group, and (3) only a polyisocyanate having a hydrophilic group. In the present invention, the hydrophilic group refers to an anionic group, a cationic group, or a nonionic group. As the water-dispersible polyisocyanate compound, it is particularly preferable that it is a polyisocyanate having a hydrophilic group.

[0209] The above-mentioned hydrophobic polyisocyanate has no hydrophilic group. For example, aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2-isocyanatoethyl (2,6-diisocyanato) hexanoate; alicyclic diisocyanates such as 1,3-bis(isocyanatomethylcyclohexane), 1,4-bis(isocyanatomethylcyclohexane), 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl(3-isocyanatomethyl) cyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5-diisocyanatomethylnorbornane, 2,6-diisocyanatomethylnorbornane; alicyclic triisocyanates such as 2,5-diisocyanatomethyl-2-isocyanopropylnorbornane, 2,6-diisocyanatomethyl-2-isocyanopropylnorbornane; aralkylene diisocyanates such as m-xylylene diisocyanate, α,α,α',α'-tetramethyl-m-xylylene diisocyanate; aromatic diisocyanates such as m- or p-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate; aromatic triisocyanates such as triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate; polyisocyanates having a uretdione structure obtained by cyclodimerization of the isocyanate groups of the above-mentioned diisocyanates or triisocyanates;Polyisocyanates having an isocyanurate structure obtained by cyclotrimerizing the isocyanate groups of the above diisocyanates or triisocyanates; polyisocyanates having a biuret structure obtained by reacting the above diisocyanates or triisocyanates with water; polyisocyanates having an oxadiazinetrione structure obtained by reacting the above diisocyanates or triisocyanates with carbon dioxide; polyisocyanates having an allophanate structure, etc. Among these, polyisocyanates having an isocyanurate structure are preferred because they can form a dense crosslinked coating film and further improve the alcohol resistance of the cured coating film.;

[0210] Examples of the polyisocyanate having the hydrophilic group include polyethers, polyesters, polyurethanes, vinyl polymers, alkyd resins, fluororesins, silicone resins, etc. having a hydrophilic group and an isocyanate group. Among these, polyethers or vinyl polymers having a hydrophilic group and an isocyanate group are preferred because of their good water dispersibility, and polyethers having a hydrophilic group and an isocyanate group are more preferred. These polyisocyanates having a hydrophilic group can be used alone or in combination of two or more kinds.;

[0211] Examples of commercially available products of the water-dispersible polyisocyanate compound include Bayhydur XP 2700 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Bayhydur 3100 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc.;

[0212] Among the above polyisocyanate compounds, Desmodur N3390 (manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO content 19.6%), Takenate D120N (manufactured by Mitsui Chemicals, Inc., NCO content 11%), Sumidur N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd., isocyanurate structure of hexamethylene diisocyanate) are more preferred.;

[0213] The composition of the present disclosure further contains a polyisocyanate compound, and it is preferable that the equivalent ratio (NCO / OH) of the isocyanate groups (NCO) of the polyisocyanate compound to the hydroxyl groups (OH) of the modified polymer is less than 1.0.

[0214] As the above equivalent ratio, since better adhesion and abrasion resistance can be obtained, it is preferably 0.90 or less, more preferably 0.85 or less, preferably 0.20 or more, and more preferably 0.30 or more.

[0215] It is also preferable that the above composition further contains a resin other than the modified polymer. Examples of other resins include polystyrene, (meth)acrylic resins, polyester resins, alkyd resins, melamine-formaldehyde resins, polyisocyanate resins, epoxy resins, vinyl chloride resins (such as vinyl chloride-vinyl acetate copolymers), ketone resins, petroleum resins, and organic resins such as chlorinated polyolefins such as polyethylene and polypropylene; inorganic resins such as silica gel and silicic acid; various fluorine resins other than the modified polymer (such as homopolymers of tetrafluoroethylene and chlorotrifluoroethylene or copolymers of these with other monomers). The proportion of other resins is 900 parts by mass or less, preferably 500 parts by mass or less, based on 100 parts by mass of the modified polymer. The lower limit is the amount necessary to obtain the desired properties and is determined by the type of resin. In the case of (meth)acrylic resins, it is usually 5 parts by mass or more, preferably 10 parts by mass or more.

[0216] Among these resins, it is preferable that the above composition contains a (meth)acrylic resin having particularly excellent compatibility, which gives the resulting coating film high gloss, high hardness, and good finish appearance.

[0217] Examples of the (meth)acrylic resin include (meth)acrylic polymers that have been conventionally used for paints. In particular, (i) homopolymers or copolymers of alkyl esters of (meth)acrylic acid having 1 to 10 carbon atoms, and (ii) (meth)acrylate copolymers having curable functional groups in side chains and / or at the main chain terminals are preferably employed.

[0218] Examples of the (meth)acrylic polymer of the above (i) include homopolymers and copolymers of alkyl esters of (meth)acrylic acid having 1 to 10 carbon atoms, such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or copolymers thereof with ethylenically unsaturated monomers copolymerizable therewith.

[0219] Examples of the ethylenically unsaturated monomers copolymerizable therewith include (meth)acrylates having an aromatic group, (meth)acrylates having a fluorine atom or a chlorine atom at the α-position, fluoroalkyl (meth)acrylates in which the alkyl group is substituted with a fluorine atom, vinyl ethers, vinyl esters, aromatic vinyl monomers such as styrene, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, diesters of fumaric acid, diesters of maleic acid, (meth)acrylonitrile, and the like.

[0220] Examples of the (meth)acrylic polymer in (ii) above include those obtained by copolymerizing a monomer having a curable functional group together with the monomer that gives the (meth)acrylic polymer described in (i) above. Examples of the monomer containing a curable functional group include monomers having a hydroxyl group, a carboxyl group, an epoxy group, an amino group, etc. Specific examples of the (meth)acrylic polymer in (ii) above include, for example, copolymers of monomers having a curable functional group such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl vinyl ether, (meth)acrylic acid, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, etc. and alkyl esters of (meth)acrylic acid having 1 to 10 carbon atoms, or copolymers of these and ethylenically unsaturated monomers copolymerizable therewith, but are not limited thereto.

[0221] The number average molecular weight of the (meth)acrylic polymer is preferably 1000 to 200000 as measured by GPC, more preferably 2000 to 100000. When it becomes larger, the solvent solubility tends to decrease, and when it becomes smaller, problems tend to occur in weather resistance.

[0222] The above composition may further contain an additive. Examples of the additive include a curing accelerator, a pigment, a dispersant, a fluidity improver, a leveling agent, an antifoaming agent, a gelation inhibitor, an ultraviolet absorber, an antioxidant, a hydrophilizing agent, a matting agent, an adhesion improver, a flame retardant, etc.

[0223] Examples of the above-mentioned pigment include titanium dioxide. The above-mentioned titanium dioxide is not particularly limited and may be either rutile type or anatase type, but rutile type is preferred in terms of weather resistance. Further, as the above-mentioned titanium dioxide, it may be titanium dioxide obtained by subjecting the surface of titanium dioxide fine particles to inorganic treatment, organic treatment, or treatment with both inorganic and organic substances. Examples of the inorganic-treated titanium dioxide include those obtained by coating the surface of titanium dioxide fine particles with alumina (Al2O3), silica (SiO2), or zirconia (ZrO2). Examples of the organic-treated titanium dioxide include those surface-treated with a silane coupling agent, those surface-treated with an organic siloxane, those surface-treated with an organic polyol, those surface-treated with an alkylamine, and the like. Furthermore, it is preferable that the titanium dioxide has a base value obtained by titration that is higher than the acid value.

[0224] Examples of commercially available products of the above-mentioned titanium dioxide include D-918 (manufactured by Sakai Chemical Industry Co., Ltd.), R-960, R-706, R-931 (manufactured by DuPont), PFC-105 (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

[0225] The content of the above-mentioned titanium dioxide is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the modified polymer. If it is less than 1 part by mass, there is a risk that ultraviolet rays cannot be blocked. If it exceeds 500 parts by mass, there is a risk of yellowing and deterioration due to ultraviolet rays. The content of the above-mentioned titanium dioxide is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less.

[0226] Examples of the above-mentioned pigment also include carbon black. The above-mentioned carbon black is not particularly limited and includes generally known ones. In terms of the ultraviolet ray shielding effect, the average particle diameter of the above-mentioned carbon black is preferably 10 to 150 nm, and more preferably 20 to 100 nm. The above-mentioned average particle diameter is a value obtained by observation with an electron microscope.

[0227] The above carbon black may be aggregated in the above composition. In this case, the average particle size is preferably 50 to 1000 nm, more preferably 100 to 700 nm, and even more preferably 100 to 500 nm from the viewpoint of the ultraviolet shielding effect. The above average particle size is a value obtained by measurement with a laser diffraction / scattering particle size distribution analyzer.

[0228] The content of the above carbon black is preferably 0.5 to 80 parts by mass with respect to 100 parts by mass of the modified polymer. When the content of the carbon black is within the above range, it can be well dispersed in the above composition. The content of the above carbon black is more preferably 3 parts by mass or more, even more preferably 10 parts by mass or more, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less with respect to 100 parts by mass of the modified polymer. Examples of commercially available products of the above carbon black include MA-100 (manufactured by Mitsubishi Chemical Corporation), Raven-420 (manufactured by Columbian Carbon Company), and the like.

[0229] When the above composition contains the above pigment, it is preferably further contained with a dispersant or a fluidity improver described later.

[0230] Examples of the above dispersant include compounds having an acid group (excluding those having an unsaturated group). Examples of the above acid group include a phosphate group, a carboxylic acid group, a sulfonic acid group, and the like. Among them, it is preferably at least one selected from the group consisting of a phosphate group and a carboxylic acid group, and more preferably a phosphate group, in terms of preventing aggregation of the pigment over a longer period and having excellent storage stability of the above composition. The above dispersant also consists of a compound having no unsaturated group. Since it has no unsaturated group, the compound is less likely to be modified by ultraviolet exposure.

[0231] The above dispersant preferably has a weight average molecular weight of 300 to 1,000,000. If it is less than 300, the steric stabilization of the adsorbed resin layer is insufficient, and there is a risk that the aggregation of titanium dioxide cannot be prevented. If it exceeds 1,000,000, there is a risk of color separation and a decrease in weather resistance. The above weight average molecular weight is more preferably 1,000 or more, and more preferably 100,000 or less. The above weight average molecular weight can be measured by gel permeation chromatography (GPC) (in terms of polystyrene).

[0232] The above dispersant preferably has an acid value of 3 to 2000 mgKOH / g in terms of effectively adsorbing on the surface of titanium dioxide. The acid value is more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, more preferably 1000 mgKOH / g or less, and still more preferably 500 mgKOH / g or less. The above acid value can be measured by an acid-base titration method using a basic substance.

[0233] The above dispersant may further contain a base. Examples of the above base include an amino group and the like.

[0234] The base value of the above dispersant is preferably 15 mgKOH / g or less, and more preferably 5 mgKOH / g or less in terms of good long-term storage stability of the dispersant. When the acid value of the above dispersant is 15 mgKOH / g or less, the base value is more preferably less than 5 mgKOH / g. The above dispersant is more preferably substantially free of a base. Note that substantially free of a base means that considering contamination, reaction residues, measurement errors, etc., the base value is 0.5 mgKOH / g or less as a measured value. The above base value can be measured by an acid-base titration method using an acidic substance.

[0235] As the above dispersant, commercially available products may be used. For example, Disparon 2150, Disparon DA-325, DA-375, DA-1200 (trade names, manufactured by Kusumoto Chemical Co., Ltd.), Flowlen G-700, G-900 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE 26000, 32000, 36000, 36600, 41000, 55000 (trade names, manufactured by Lubrizol Japan Ltd.), DISPERBYK-102, 106, 110, 111, 140, 142, 145, 170, 171, 174, 180 (trade names, manufactured by BYK Japan Co., Ltd.), etc. can be mentioned. Among them, Disparon DA-375, Flowlen G-700, and SOLSPERSE 36000 are preferable in terms of good long-term storage stability, and Disparon DA-375 is more preferable.

[0236] The above dispersant is preferably used together with the above titanium dioxide. The content of the above dispersant is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of titanium dioxide. If it is less than 0.1 part by mass, there is a possibility that the effect of preventing pigment sedimentation cannot be obtained. If it exceeds 100 parts by mass, there is a possibility of causing color separation and a decrease in weather resistance. The content of the above dispersant is more preferably 0.5 part by mass or more, still more preferably 1.5 parts by mass or more, more preferably 50 parts by mass or less, and still more preferably 20 parts by mass or less.

[0237] As the above fluidity improver, an associative acrylic polymer having an acid group and a base can be mentioned. The above associative acrylic polymer is one in which polar groups contained in the acrylic polymer chain form a structure due to partial adsorption or the like by hydrogen bonding or electrical interaction within the polymer chain or between polymer chains, and as a result, has the effect of increasing the viscosity of the liquid.

[0238] Examples of the acrylic polymer include copolymers composed of (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, cyclohexyl (meth)acrylate, etc. as the main monomer components. Note that "(meth)acrylate" includes acrylate and methacrylate.

[0239] As the above acid group, a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group are preferable. Among them, a carboxylic acid group is preferable in terms of preventing aggregation of the pigment over a longer period and maintaining the storage stability of the above composition. Examples of the above base include an amino group.

[0240] Further, the above fluidity improver may be a reaction product of a carboxylic acid and a nitrogen-containing compound of hydroxyamine or hydroxyimine. The ratio of the carboxylic acid and the nitrogen-containing compound to be reacted is most preferably 1:1. Examples of the carboxylic acid include dicarboxylic acids and acid anhydrides. Examples of the above hydroxyamine include primary, secondary, and tertiary alkanolamines such as monoethanolamine, propanolamine, diethanolamine, triethanolamine, n-butyldiethanolamine, etc. and mixtures thereof. Examples of the above hydroxyimine include those having an oxazoline structure, specifically, Alkaterge T (trade name, manufactured by Angus Chemical Co.).

[0241] The above-mentioned fluidity improver preferably has a weight average molecular weight of 1,000 to 1,000,000. If it is less than 1,000, insufficient structure formation due to aggregation may prevent the precipitation of titanium dioxide. If it exceeds 1,000,000, the viscosity of the liquid may increase too much, possibly impairing the paintability. More preferably, the above weight average molecular weight is 5,000 or more, and even more preferably 100,000 or less. The above weight average molecular weight can be measured by gel permeation chromatography (GPC) (in terms of polystyrene).

[0242] As the above-mentioned fluidity improver, commercially available products may be used. For example, SOLTHIX 250 (trade name, manufactured by Nippon Lubrizol Corporation) etc. can be mentioned.

[0243] The content of the above-mentioned fluidity improver is preferably 0.05 to 20% by mass in the above composition. If it is less than 0.05% by mass, there is a risk that the precipitation of titanium dioxide cannot be prevented. If it exceeds 20% by mass, there is a risk of separation or color separation. More preferably, the content of the above fluidity improver is 0.1% by mass or more, even more preferably 0.3% by mass or more, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0244] As the above-mentioned flame retardant, it is preferably one that generates a non-combustible gas in the initial stage of combustion and exhibits flame retardancy by diluting the combustible gas and / or blocking oxygen.

[0245] As the above-mentioned flame retardant, it is preferably at least one selected from the group consisting of compounds containing Group 5B of the periodic table and compounds containing halogen compounds of Group 7B of the periodic table.

[0246] Examples of compounds containing halogen compounds of Group 7B of the periodic table include aliphatic, alicyclic, and aromatic organic halogen compounds, such as bromine-based tetrabromobisphenol A (TBA), decabromodiphenyl ether (DBDPE), octabromodiphenyl ether (OBDPE), TBA epoxy / phenoxy oligomer, brominated crosslinked polystyrene, chlorine-based chlorinated paraffin, perchlorocyclopentadecane, and the like.

[0247] Examples of compounds containing Group 5B of the periodic table include phosphorus compounds such as phosphate esters and polyphosphate salts. In addition, antimony compounds are preferably used in combination with halogen compounds, such as antimony trioxide and antimony pentoxide. In addition, aluminum hydroxide, magnesium hydroxide, and molybdenum trioxide can also be used. These flame retardants can be arbitrarily selected in at least one kind and blending amount according to the type of modified polymer, and are not limited thereto.

[0248] Specifically, as the above flame retardant, a phosphorus-nitrogen-containing composition (A) or a mixture (B) of a bromine-containing compound and an antimony-containing compound is more preferable. By combining these flame retardants with the modified polymer, high flame retardancy is exhibited.

[0249] The above phosphorus-nitrogen-containing composition (A) is preferably a mixture of piperazine pyrophosphate and melamine cyanurate. Examples of piperazine pyrophosphate include those disclosed in JP-A-48-088791 and US Patent No. 4,599,375. Examples of melamine cyanurate include those obtained by pulverizing the reaction product of melamine and cyanuric acid. The reaction product of melamine and cyanuric acid has a large amount of nitrogen atoms in its structure and exhibits the function of generating nitrogen gas and inhibiting combustion when exposed to a high temperature of about 350 °C or higher.

[0250] The above phosphorus-nitrogen-containing composition (A) preferably has a mass ratio of melamine cyanurate to the above piperazine pyrophosphate in the range of 0.014 to 3.000. When the melamine cyanurate is within the above range, the flame retardancy is improved and the blocking property of the coating film is also good. The mass ratio of melamine cyanurate to the above piperazine pyrophosphate is more preferably 0.04 or more in the mixture, still more preferably 0.1 or more, more preferably 1.4 or less, and still more preferably 0.5 or less.

[0251] Examples of commercially available products that can be used as the above phosphorus-nitrogen-containing composition (A) include SCFR-200 (manufactured by Sakai Chemical Industry Co., Ltd.), SCFR-110 (manufactured by Sakai Chemical Industry Co., Ltd.), and the like.

[0252] The above bromine-containing compound is preferably an aromatic compound having a bromine content of 65% or more, a melting point of 200 °C or more, and a 5% decomposition temperature of 340 °C or more. Specifically, the above bromine-containing compound is preferably at least one selected from the group consisting of decabromodiphenyl oxide, 1,2-bis(2,3,4,5,6-pentabromophenyl)ethane, tris(tribromophenoxy)triazine, ethylenebistetrabromophthalimide, polybromophenyl indane, brominated phenylene oxide, and polypentabromobenzyl acrylate.

[0253] Among them, 1,2-bis(2,3,4,5,6-pentabromophenyl)ethane represented by the formula (a) is more preferable in that it has a high melting point and does not melt or bleed out even when the coating film is heat-cured.

Chemical formula

[0254] As the above bromine-containing compound, commercially available products may be used. For example, SAYTEX8010 (manufactured by Albemarle Corporation) and the like can be mentioned.

[0255] Examples of the antimony-containing compound include antimony oxides such as antimony trioxide and antimony pentoxide. Among them, antimony trioxide is preferred in terms of being available at low cost.

[0256] The content of the flame retardant is preferably 1 to 45 parts by mass with respect to 100 parts by mass of the modified polymer. When the content of the flame retardant is within the above range, good dispersibility in the composition and improvement in the flame retardancy of the coating film obtained from the composition can be expected. If the content of the flame retardant is less than 1 part by mass, improvement in flame retardancy may not be expected, and if it exceeds 45 parts by mass, it may be difficult to maintain the physical properties of the composition and the coating film. The content of the flame retardant is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less with respect to 100 parts by mass of the modified polymer. Also, 3 parts by mass or more is more preferable, and 5 parts by mass or more is still more preferable.

[0257] When the flame retardant is the phosphorus-nitrogen-containing composition (A), its content is preferably 8 to 19 parts by mass with respect to 100 parts by mass of the modified polymer. The content of the phosphorus-nitrogen-containing composition (A) is more preferably 9 parts by mass or more, still more preferably 10 parts by mass or more, more preferably 17 parts by mass or less, and still more preferably 15 parts by mass or less with respect to 100 parts by mass of the modified polymer.

[0258] When the flame retardant is the mixture (B) of the bromine-containing compound and the antimony-containing compound, its content is preferably such that the content of the bromine-containing compound is 1 to 30 parts by mass and the content of the antimony-containing compound is 0.5 to 15 parts by mass with respect to 100 parts by mass of the modified polymer. The content of the bromine-containing compound is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less with respect to 100 parts by mass of the modified polymer. The content of the antimony compound is more preferably 1.5 parts by mass or more, still more preferably 2.5 parts by mass or more, more preferably 10 parts by mass or less, and still more preferably 7.5 parts by mass or less with respect to 100 parts by mass of the modified polymer.

[0259] Examples of the above-mentioned curing accelerators include organotin compounds, acidic phosphate esters, reaction products of acidic phosphate esters and amines, saturated or unsaturated polycarboxylic acids or their acid anhydrides, organic titanate compounds, amine compounds, lead octylate, and the like.

[0260] Specific examples of the above-mentioned organotin compounds include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate, dibutyltin phthalate, tin octylate, tin naphthenate, dibutyltin methoxide, and the like.

[0261] The above-mentioned acidic phosphate ester refers to

Chemical formula

[0262] Specifically,

Chemical formula

[0263] Examples of the above-mentioned organic titanate compounds include titanate esters such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate. Commercially available products include, for example, Organicx TC-100, TC-750, TC-760, TA-30 manufactured by Matsumoto Fine Chemical Co., Ltd.

[0264] Furthermore, specific examples of the above amine compounds include, for example, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo(5.4.0)undecene-7 (DBU), and furthermore salts such as their carboxylic acids, low molecular weight polyamide resins obtained from excess polyamine and polybasic acid, reaction products of excess polyamine and epoxy compounds, and the like.

[0265] The above curing accelerator may be used alone or in combination of two or more. The blending ratio of the above curing accelerator is preferably about 1.0×10 -6 to 1.0×10 -2 parts by mass, more preferably about 5.0×10 -5 to 1.0×10 -3 parts by mass with respect to 100 parts by mass of the modified polymer.

[0266] Specific examples of the pigment include, for example, inorganic pigments such as titanium dioxide, calcium carbonate or carbon black; organic pigments such as phthalocyanine-based, quinacridone-based or azo-based pigments, etc., but are not limited thereto. The upper limit of the addition amount of the pigment is usually up to about 200 parts by mass with respect to 100 parts by mass of the modified polymer.

[0267] As the above hydrophilizing agent, methyl silicate, ethyl silicate, fluoroalkyl silicate, and condensates thereof can be used. Commercially available products include, for example, ET40, ET48 manufactured by Colcoat Co., Ltd., MS56, MS56S, MS57 manufactured by Mitsubishi Chemical Corporation, GH700, GH701 manufactured by Daikin Industries, Ltd., and the like.

[0268] Examples of the above-mentioned matting agent include silica, silica alumina, alumina, talc, calcium carbonate, titanium dioxide, etc. The addition amount of the above-mentioned matting agent is preferably 1 to 100% by mass based on the modified polymer. Examples of commercially available products include Silicia 350, Silicia 436, Silicia 446, Silohobic 100, Silohobic 200 manufactured by Fuji Silysia Chemical Ltd., and Siloid ED2, Siloid ED30, Siloid ED50 manufactured by Grace Co., Ltd.

[0269] Examples of the above-mentioned adhesion improver include various polyol-based additives such as polyester polyol, polycarbonate polyol, polyether polyol, polybutadiene polyol, and silane coupling agent. The addition amount of the above-mentioned adhesion improver is preferably 0.1 to 50% by mass based on the modified polymer. Examples of commercially available products include Flexorez 148, Flexorez 188, Flexorez A308 manufactured by Kusumoto Chemicals, Ltd., ETERNACOLL UH-50, ETERNACOLL UM-90 manufactured by Ube Industries, Ltd., Adeka Polyether P-400, Adeka Polyol BPX-21 manufactured by ADEKA Corporation, NISSO-PB GI-1000, GI-2000, GI-3000 manufactured by Nippon Soda Co., Ltd., PH-50, PH-100 manufactured by Ube Industries, Ltd., Priplast-1838, Priplast-3192 manufactured by Croda Japan Co., Ltd.

[0270] The above composition can be directly applied to metals, concrete, plastics, etc. or over primer paints such as wash primer, rust preventive paint, epoxy paint, acrylic resin paint, polyester resin paint, or on the coating specifications of primer / undercoat as paints for indoor use such as building materials and interior materials, or for outdoor use such as building materials, automobiles, airplanes, ships (decks, decks, ship bottoms, etc.), trains, tanks, bridges, etc. Furthermore, it can also be used as a sealing agent or a film-forming agent.

[0271] The above composition or the film obtained from the above composition can be applied to substrates made of metal, concrete, plastic, stone, wood, paper, etc. Further, it can also be applied to the substrate with an intervening primer layer or undercoat layer. As the above primer, known primers can be used, and examples thereof include epoxy primers and zinc-rich primers. Examples of the paint for forming the above undercoat include acrylic paints, urethane paints, polyester paints, epoxy paints, and the like.

[0272] In addition to the above, the above composition can be applied, for example, as a coating agent or antifouling agent (such as a coating film that is not easily soiled outdoors or a coating agent whose dirt can be easily wiped off) for solar cell backsheets and front sheets, golf balls, etc., or as a coating film or coating agent having algae-proof or antibacterial activity.

[0273] The present disclosure also provides a coating film characterized by containing the above modified polymer. Due to this feature, the above coating film is excellent in antifouling properties. It is also excellent in weather resistance and the like. Furthermore, it is excellent in adhesion to the substrate. The above coating film is preferably a cured coating film.

[0274] The present disclosure also provides a coating film obtained by applying the above composition. Due to this feature, the above coating film is excellent in antifouling properties. It is also excellent in weather resistance and the like. Furthermore, it is excellent in adhesion to the substrate.

[0275] The above coating film can be formed by applying the above composition to a substrate or the like and drying and curing it as desired. The above drying and curing can be carried out at 10 to 300 °C, usually 100 to 200 °C, for 30 seconds to 3 days. After the above drying and curing, curing may be carried out, and the above curing is usually completed at 20 to 300 °C for 1 minute to 3 days.

[0276] The above-mentioned coating film preferably has a film thickness of 5 μm or more from the viewpoints of good hiding property, weather resistance, chemical resistance, and moisture resistance. More preferably, it is 7 μm or more, and still more preferably, it is 10 μm or more. The upper limit is preferably about 1000 μm, more preferably about 100 μm, because if it is too thick, the weight reduction effect cannot be obtained. Particularly, the film thickness is preferably 10 to 40 μm.

[0277] The above-mentioned coating film preferably has a water contact angle of 95° or more and a gloss retention rate of 80% or more after 3000 hours of QUVB. The water contact angle is more preferably 97° or more, and still more preferably 99° or more. The gloss retention rate after 3000 hours of QUVB is preferably 85% or more, more preferably 90% or more. The above-mentioned coating film preferably has a water contact angle of 80° or more after 1000 hours of QUVB, more preferably 85° or more, and still more preferably 90° or more. The above-mentioned coating film preferably has an oil contact angle of 10° or more, more preferably 15° or more, and still more preferably 50° or more. The above-mentioned coating film further preferably has an oil contact angle of 25° or more after 1000 hours of QUVB, more preferably 30° or more, and still more preferably 40° or more.

[0278] The above-mentioned coating film can be provided on various substrates. A primer layer may be provided between the substrate and the coating film, but since the coating film has excellent adhesion, it is possible to directly adhere the substrate and the coating film with sufficient adhesive strength. The laminate including the coating film and the substrate is also one of the preferred embodiments of the present disclosure.

[0279] Examples of the material of the substrate include metal, ceramic, resin, glass, etc.

[0280] Examples of the above-mentioned metal include iron; stainless steels such as SUS304, SUS316L, and SUS403; aluminum; and plated steel sheets plated with zinc, aluminum, etc. Examples of the above-mentioned ceramic include pottery, porcelain, alumina materials, zirconia materials, and silica oxide materials. Examples of the above-mentioned resin include polyethylene terephthalate resin, polycarbonate resin, silicone resin, fluorosilicone resin, polyamide resin, polyamideimide resin, polyimide resin, polyester resin, epoxy resin, polyphenylene sulfide resin, phenol resin, acrylic resin, and polyethersulfone resin.

[0281] As the above-mentioned base material, a water-impermeable sheet can also be used. The above-mentioned water-impermeable sheet is a layer provided so that moisture does not permeate through the member, and any material that does not substantially allow water to permeate can be used. Examples of the material of the above-mentioned water-impermeable sheet include, for example, polycarbonate resin, acrylic resin, methacrylic resin, ABS resin, polyolefin resin (such as polyethylene and polypropylene), polyvinyl halide resin (such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride), polyester resin (such as polyethylene terephthalate and polybutylene terephthalate), polyamide resin (such as nylon 6, nylon 66, and MXD nylon (meta-xylenediamine-adipic acid copolymer)), polymers of olefins having substituents (such as polyvinyl acetate and polyvinyl alcohol), copolymers such as EVA (ethylene-vinyl alcohol copolymer) and ethylene-tetrafluoroethylene copolymer. Two or more of these materials may be used in combination.

[0282] Examples of the material of the above-mentioned base material included in the above-mentioned laminate include the materials described above, and among them, polyethylene terephthalate resin is preferable.

[0283] The above laminate can be used for building materials, interior materials, automobiles, aircraft, ships (such as decks, decks, ship bottoms), trains, tanks, bridges, etc. Since the laminate of the present disclosure is excellent in weather resistance and water and oil repellency, it is extremely useful as a building material, for example. The laminate of the present disclosure is also excellent in weather resistance and water and oil repellency, and is also excellent in the durability of weather resistance and water and oil repellency. Therefore, it is extremely useful for anti-icing applications and anti-frosting applications that take advantage of water repellency. In anti-icing applications and anti-frosting applications, for example, it can be suitably used as the anti-fouling of the blades of wind power generation, the EPDM of the railway vehicle coupling part, the anti-fouling and anti-icing of the road bridge guide plate, the anti-icing of the transmission line, and the anti-frosting delay of the air conditioner heat exchanger.

[0284] The above laminate can also be suitably used as the backsheet of a solar cell module.

Examples

[0285] Next, the present disclosure will be described with reference to examples, but the present disclosure is not limited to such examples.

[0286] Each numerical value in the examples was measured by the following methods.

[0287] Content of each monomer unit constituting the polymer Fluorine content (mass %) measured by elemental analysis and 1 The content (mol %) of each monomer unit was calculated from the composition analysis by HNMR spectrum.

[0288] Hydroxyl value Calculated from the actual charged amount of the hydroxyl group-containing monomer and the solid content concentration during polymerization.

[0289] Synthesis Reference Example 1 (Fluorine-containing Polymer 1) Into a 6000 ml stainless steel autoclave, 2891 g of butyl acetate, 638.0 g of vinyl neodecanoate, and 156.7 g of 4-hydroxybutyl vinyl ether (HBVE) were charged. An operation of replacing with nitrogen under reduced pressure was performed, and 481.7 g of tetrafluoroethylene (TFE) was charged. 12.5 g of a peroxide-based polymerization initiator was charged to initiate polymerization. At the same time, a mixture of 639.0 g of vinyl neodecanoate and 156.7 g of HBVE was continuously charged over 1.5 hours. The reaction was carried out for 3 hours after charging the initiator at that temperature, and an additional 12.5 g of the peroxide-based polymerization initiator was charged. Further, the reaction was carried out for 4 hours at that temperature. When the reactor internal pressure decreased from 1.4 MPaG (14.5 kgf / cm 2 G) to 0.2 MPaG (2.1 kgf / cm 2 G), the reaction was stopped to obtain a solution containing the polymer. The hydroxyl value of the obtained polymer was 63 mg KOH / g.

[0290] Synthesis Reference Example 2 (Fluorine-containing Polymer 2) Into a 6000 ml stainless steel autoclave, 2500 g of butyl acetate, 584 g of vinyl neodecanoate, and 527 g of 4-hydroxybutyl vinyl ether (HBVE) were charged. An operation of replacing with nitrogen under reduced pressure was performed, and 658 g of tetrafluoroethylene (TFE) was charged. 30 g of a peroxide-based polymerization initiator was charged to initiate polymerization. When the reactor internal pressure decreased from 1.0 MPaG to 0.4 MPaG, the reaction was stopped to obtain a solution containing the polymer. The hydroxyl value of the obtained polymer was 130 mg KOH / g.

[0291] Synthesis Reference Example 3 (Fluorine-containing Polymer 3) After nitrogen substitution of a 6000 ml stainless steel autoclave, 2000 g of butyl acetate, 196.0 g of vinyl acetate, 55.2 g of 4-hydroxybutyl vinyl ether (HBVE), and 5.6 g of undecylenic acid were added. Then, 400 g of chlorotrifluoroethylene was charged. 9.6 g of a peroxide-based polymerization initiator was charged to initiate the reaction. After 6 hours from the start of polymerization, the inside of the tank was returned to normal temperature and pressure to stop the polymerization, and a solution containing the polymer was obtained. The hydroxyl value of the obtained polymer was 50 mg KOH / g, and the acid value was 3.2 mg KOH / g.

[0292] Synthesis Reference Example 4 (F monomer-1 homopolymer) 90 g of butyl acetate was added to a 1 L reaction vessel, heated to 90 °C, and stirred for 30 minutes. Then, a mixed solution of F monomer-1 (6.5 g), a chain transfer agent (0.0975 g), an initiator (0.0845 g), and butyl acetate (15 g) was added dropwise over 1 hour. Then, it was stirred at 90 °C for 2 hours to synthesize the polymer solution of Synthesis Reference Example 4. The above F monomer-1 is a compound represented by CH2=CHCOOCH2CH2C6F 13 and is a compound represented by the formula.

[0293] Synthesis Reference Example 5 (Si monomer-1 homopolymer) 90 g of butyl acetate was added to a 1 L reaction vessel, heated to 90 °C, and stirred for 30 minutes. Then, a mixed solution of Si monomer-1 (3.9 g), a chain transfer agent (0.0429 g), an initiator (0.0507 g), and butyl acetate (15 g) was added dropwise over 1 hour. Then, it was stirred at 90 °C for 2 hours to synthesize the polymer solution of Synthesis Reference Example 5. The above Si monomer-1 is a compound represented by the following formula.

Chemical formula

[0294] Synthesis Reference Example 6 (Ac-F polymer) 1-Butyl acetate (90 g) was added to a 1-L reaction vessel, and the temperature was raised to 90°C and stirred for 30 minutes. Then, a mixed solution of F monomer-1 (6.5 g), 4-hydroxybutyl acrylate (HBA) (1.3 g) as a hydroxyl group-containing monomer, glycidyl methacrylate (GMA) (1.3 g) as an epoxy group-containing monomer, a chain transfer agent (0.1365 g), an initiator (0.1183 g), and 1-butyl acetate (15 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90°C for 2 hours to synthesize the polymer solution of Synthesis Reference Example 6.

[0295] Synthesis Reference Example 7 (Ac-Si Polymer) 1-Butyl acetate (90 g) was added to a 1-L reaction vessel, and the temperature was raised to 90°C and stirred for 30 minutes. Then, a mixed solution of Si monomer-1 (3.9 g), hydroxyl group-containing monomer HBA (0.78 g), a chain transfer agent (0.05148 g), an initiator (0.06048 g), and 1-butyl acetate (15 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90°C for 2 hours to synthesize the polymer solution of Synthesis Reference Example 7.

[0296] Example 1 Fluorine-containing polymer 1 (200 g) of the reactant solution for the main chain and 1-butyl acetate (20 g) were added to a 1-L reaction vessel, and the temperature was raised to 90°C and stirred for 30 minutes. Then, a mixed solution of side chain reactant F monomer-1 (6.5 g), a chain transfer agent (0.0975 g), an initiator (0.0845 g), and 1-butyl acetate (15 g) was added dropwise over 1 hour. Thereafter, the mixture was stirred at 90°C for 2 hours to synthesize the polymer solution of Example 1. Thereafter, according to the conditions described in the table, a curing agent Desmodur N3390 (12 g) and 1-butyl acetate (40 g) manufactured by Sumitomo Bayer Urethane Co., Ltd. were added to the synthesized polymer solution (100 g), stirred at room temperature for 30 minutes, then applied to a tin plate, dried at 80°C for 3 hours, and a coating plate for evaluation with a dry film thickness of 25 μm was prepared, and various evaluations described separately were performed.

[0297] Example 2 In the synthesis of the polymer solution, except that to a mixed solution of the side chain reactant F monomer-1 (6.5 g), chain transfer agent (0.1365 g), initiator (0.1183 g), and butyl acetate (15 g), HBA (1.3 g) as a hydroxyl group-containing monomer and GMA (1.3 g) as an epoxy group-containing monomer were further added and the mixed solution was added dropwise, the synthesis of the polymer solution, preparation of the coated plate, and various evaluations were carried out in the same manner as in Example 1.

[0298] Examples 3 to 17 Except that each material was changed to the types and amounts described in Tables 1 to 2, the synthesis of the polymer solution, preparation of the coated plate, and various evaluations were carried out in the same manner as in Example 1 or 2. Note that F monomer-2 is a compound represented by CH2=C(CH3)COOCH2CH2C6F 13 and is represented by the formula. Si monomer-2 is a compound represented by the following formula. [Chemical formula] (In the formula, R1 is a hydrogen atom, R2 is CH3, and the average value of n is 160)

[0299] Comparative Examples 1 to 5 Based on 100 parts by mass of the solid content of fluorine-containing polymer 1, fluorine-containing polymer 2, fluorine-containing polymer 3, Ac-F polymer, or Ac-Si polymer, a paint was obtained so as to be a curing agent and a diluent at the ratios described in Table 1, and a coated plate was prepared and various evaluations were carried out.

[0300] Comparative Example 6 According to the conditions described in Table 3, 200 g of fluorine-containing polymer 1 was added to a 1 L reaction vessel, heated to 90°C, and stirred for 30 minutes. Then, 10 g of F monomer-1 homopolymer was added dropwise over 1 hour. Then, it was stirred at 90°C for 2 hours to prepare the polymer solution of Comparative Example 6. Then, according to the conditions described in Tables 1 to 3, to 100 g of the prepared polymer solution, 12 g of curing agent N3390 and 40 g of butyl acetate were added, stirred at room temperature for 30 minutes, applied to a tin plate, dried at 80°C for 3 hours, and a coated plate for evaluation with a dry film thickness of 25 μm was prepared and various evaluations described separately were carried out.

[0301] Comparative Examples 7 - 11 Except for changing the amounts of the respective materials to those described in Table 3, the preparation of the polymer solution, the preparation of the coated plates, and various evaluations were carried out in the same manner as in Comparative Example 6.

[0302] Evaluation Items Water - to - oil contact angle: The contact angle was measured using a G - 1 type contact angle measuring instrument manufactured by Kyowa Chemical Industry Co., Ltd. Wiping off of oil - based pen: Using a black oil - based marker manufactured by Zebra, after dry - wiping, the remaining marks were visually evaluated. QUVB: Using an aging acceleration tester manufactured by QLAB, a weather resistance promotion test was carried out with a cycle operation of irradiation intensity 0.63 W / cm 2 , irradiation for 4 hours (60 degrees), and non - irradiation for 4 hours. Gloss retention rate: The 60 - degree gloss was measured using AG - 4442 manufactured by BYK. Color difference: The color difference was measured using a color difference meter DP - 400 and CR - 400 manufactured by Konica.

[0303]

Table 1

[0304]

Table 2

[0305]

Table 3

Claims

1. (a) a main chain composed of a fluorine-containing polymer, (b) a side chain represented by formula (b1’) and / or formula (b2’), having, wherein the fluorine-containing polymer is a modified polymer having a unit represented by -CHR- (wherein R is a hydrogen atom or a monovalent organic group), a fluorine-containing monomer unit, a vinyl ester unit containing neither a hydroxyl group nor an aromatic ring, and a hydroxyl group-containing monomer unit, A composition containing at least one solvent selected from the group consisting of ester solvents, aliphatic hydrocarbons, alcohol solvents, and cyclic ether solvents. -CH ２ -CR ｂ１ (-X)-C(=O)-Y-Z-Rf (b1’) [wherein X is a hydrogen atom, a methyl group, or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, R ｂ１ is a hydrogen atom or a monovalent organic group. ] -CH ２ -CR ｂ２ (-R １ )-C(=O)-O-Si(-CH ３ ) ２ -[O-Si(-CH ３ ) ２ - ｎ -O-Si(-CH ３ ) ２ -R ２ (b2’) [wherein R １ is a hydrogen atom or a methyl group, R ２ is a hydrogen atom or a methyl group, R ｂ２ is a hydrogen atom or a monovalent organic group, n is 3 to 200. ]

2. The composition according to claim 1, wherein the fluorine-containing polymer contains polymerization units based on tetrafluoroethylene or chlorotrifluoroethylene.

3. The composition according to claim 1 or 2, further comprising a curing agent.

4. The composition according to any one of claims 1 to 3, which is a paint.

5. The composition according to any one of claims 1 to 4, which is an anti-freezing and / or anti-frosting composition.

6. (a) a main chain composed of a fluorine-containing polymer, (b) a side chain represented by formula (b1') and / or formula (b2'), and having, wherein the fluorine-containing polymer is a modified polymer having a unit represented by -CHR- (wherein R is a hydrogen atom or a monovalent organic group), a fluorine-containing monomer unit, a vinyl ester unit containing neither a hydroxyl group nor an aromatic ring, and a hydroxyl group-containing monomer unit, and a solvent, a paint. -CH ２ -CR ｂ１ (-X)-C(=O)-Y-Z-Rf (b1') [wherein X is a hydrogen atom, a methyl group or a halogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, R ｂ１ is a hydrogen atom or a monovalent organic group. ] -CH ２ -CR ｂ２ (-R １ )-C(=O)-O-Si(-CH ３ ) ２ -[O-Si(-CH ３ ) ２ ｎ -O-Si(-CH ３ ) ２ -R ２ (b2') [wherein R １ is a hydrogen atom or a methyl group, R ２ is a hydrogen atom or a methyl group, R ｂ２ is a hydrogen atom or a monovalent organic group, and n is from 3 to 200. ]

7. The paint according to claim 6, wherein the fluorine-containing polymer contains a polymerization unit based on tetrafluoroethylene or chlorotrifluoroethylene.

8. The paint according to claim 6 or 7, further comprising a curing agent.

9. The paint according to any one of claims 6 to 8, which is an anti-freezing and / or anti-frosting composition.

10. A coating film obtained by applying the composition according to any one of claims 1 to 5 or the paint according to any one of claims 6 to 9, wherein the hydroxyl group-containing monomer unit is Formula (A): CH₂=CH-(CH₂)ₗ-O-(CH₂)ₘ-OH (wherein l is 0 and m is an integer from 2 to 20).

11. The coating film according to claim 10, having a water contact angle of 95° or more and a gloss retention rate of 80% or more after 3000 hours of QUVB.

12. The coating film according to claim 10 or 11, having a water contact angle of 80° or more after 1000 hours of QUVB and an oil contact angle of 25° or more after 1000 hours of QUVB.

13. A laminate comprising a substrate and the coating film according to any one of claims 10 to 12.

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