Fluorine-containing polymer and fluorine-containing composition

Abstract

Provided are a fluorine-containing polymer and a fluorine-containing composition which are capable of imparting excellent dynamic water repellency at low concentrations and excellent water repellency when used as an auxiliary agent. The present invention can impart excellent dynamic water repellency to a substrate at a low concentration and excellent water repellency to a substrate when used as an auxiliary agent by using a fluorine-containing polymer having a repeating unit formed from the following monomers (a) to (d): (a) a first fluorine-containing acrylic monomer having an alpha-position chlorine atom; (b) a second fluorine-containing acrylic monomer having an alpha-position hydrogen atom or an organic group; (c) a first acrylic monomer having a chain-like hydrocarbon group having 12-40 carbon atoms; and (d) a second acrylic monomer having a C3-40 cyclic hydrocarbon group.

Description

Technical Field

[0001] The present invention relates to a fluorine-containing polymer and a fluorine-containing composition. The fluorine-containing composition can be used as a surface treatment agent. Background Art

[0002] At present, various fluorine-containing compounds have been proposed. Fluorine-containing compounds have advantages such as excellent heat resistance, oxidation resistance, weather resistance, etc. Taking advantage of the low free energy of fluorine-containing compounds, that is, the property of being difficult to adhere, fluorine-containing compounds are used, for example, in water-repellent and oil-repellent agents and antifouling agents.

[0003] Patent Document 1 (International Patent Publication No. 2018 / 084132) discloses that a fluorinated polymer formed from two different fluorinated monomers can impart excellent washing durability and water and oil repellency.

[0004] Patent Document 2 (Japanese Patent Application Laid-Open No. 2016-196651) discloses that a fluorinated polymer formed from a fluorinated monomer and a high glass transition temperature monomer has excellent water and oil repellency and is resistant to rollers during processing.

[0005] Patent Literature

[0006] Patent Document 1: International Patent Publication No. 2018 / 084132

[0007] Patent Document 2: Japanese Patent Application Publication No. 2016-196651 Summary of the invention

[0008] Problems to be solved by the invention

[0009] Patent Documents 1 and 2 do not describe the dynamic water repellency at low concentrations or the water repellency when used as an auxiliary agent.

[0010] The present invention aims to impart excellent dynamic water repellency at low concentrations and excellent water repellency when used as an auxiliary agent.

[0011] In the present invention, the "auxiliary agent" refers to the curing agent (4) and other components (5) (for example, non-fluorinated hydrophobic compounds and / or additives).

[0012] Technical solutions to solve problems

[0013] The present invention provides a fluorine-containing composition comprising the following (1) and (2),

[0014] (1) Fluorine-containing polymers,

[0015] (2) Liquid medium.

[0016] The present invention provides a fluorine-containing polymer having repeating units formed from the following first monomer (a), second monomer (b), third monomer (c) and fourth monomer (d),

[0017] a first monomer (a) which is a fluorine-containing acrylic monomer having a chlorine atom at the α-position,

[0018] The second monomer (b) is a fluorine-containing acrylic monomer having a hydrogen atom or an organic group at the α position,

[0019] The third monomer (c) is an acrylic monomer having a chain hydrocarbon group having 12 to 40 carbon atoms,

[0020] The fourth monomer (d) is an acrylic monomer having a cyclic hydrocarbon group having 3 to 40 carbon atoms.

[0021] Preferred embodiments of the present invention are as follows.

[0022] Implementation 1:

[0023] A fluorine-containing polymer having repeating units formed from the following first monomer (a), second monomer (b), third monomer (c) and fourth monomer (d),

[0024] a first monomer (a) which is a fluorine-containing acrylic monomer having a chlorine atom at the α-position,

[0025] The second monomer (b) is a fluorine-containing acrylic monomer having a hydrogen atom or an organic group at the α position,

[0026] The third monomer (c) is an acrylic monomer having a chain hydrocarbon group having 12 to 40 carbon atoms,

[0027] The fourth monomer (d) is an acrylic monomer having a cyclic hydrocarbon group having 3 to 40 carbon atoms.

[0028] Implementation 2:

[0029] The fluorinated polymer as described in embodiment 1, wherein

[0030] The weight ratio of the third monomer (a) to the fourth monomer (b) is 5:95 to 95:5.

[0031] Implementation 3:

[0032] The fluorinated polymer according to embodiment 1 or 2, wherein

[0033] The first monomer (a) is a compound represented by the following formula:

[0034] CH2=C(-X 11 )-C(=O)-Y 11 -Z 11-Rf 11

[0035] [Wherein, X 11 is a halogen atom,

[0036] Y 11 is -O- or -NH-,

[0037] Z 11 is a direct bond or a divalent organic group,

[0038] R 11 is a fluoroalkyl group having 1 to 20 carbon atoms. ],

[0039] The second monomer (b) is a compound represented by the following formula:

[0040] CH2=C(-X 12 )-C(=O)-Y 12 -Z 12 -Rf 12

[0041] [Wherein, X 12 A hydrogen atom or a monovalent organic group,

[0042] Y 12 is -O- or -NH-,

[0043] Z 12 is a direct bond or a divalent organic group,

[0044] R 12 is a fluoroalkyl group having 1 to 20 carbon atoms. ],

[0045] The third monomer (c) is a compound represented by the following formula:

[0046] CH2=C(-X 21 )-C(=O)-Y 21 -R 21

[0047] [Wherein, X 21 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0048] Y 21 is -O- or -NH-,

[0049] R 21 It is a chain hydrocarbon group having 12 to 40 carbon atoms.

[0050] The fourth monomer (d) is a compound represented by the following formula:

[0051] CH2=C(-X 22 )-C(=O)-Y 22 -R22

[0052] [Wherein, X 22 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0053] Y 22 is -O- or -NH-,

[0054] R 22 It is a cyclic hydrocarbon group having 3 to 40 carbon atoms. ].

[0055] Implementation 4:

[0056] The fluorinated polymer according to any one of Embodiments 1 to 3, wherein

[0057] The monovalent organic group is an alkyl group having 1 to 4 carbon atoms,

[0058] The divalent organic group is a linear or branched alkylene group having 1 to 20 carbon atoms.

[0059] The cyclic hydrocarbon group having 3 to 40 carbon atoms is a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 to 25 carbon atoms.

[0060] Implementation 5:

[0061] The fluorinated polymer according to any one of Embodiments 1 to 4, wherein

[0062] The third monomer (c) is:

[0063] At least one long-chain acrylate monomer selected from the group consisting of lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, lauryl α-chloroacrylate, hexadecyl α-chloroacrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate and behenyl α-chloroacrylate; or

[0064] At least one long-chain acrylamide monomer selected from the group consisting of lauryl (meth)acrylamide, hexadecyl (meth)acrylamide, stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide,

[0065] The fourth monomer (d) is:

[0066] At least one compound selected from the group consisting of cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate and 2-ethyl-2-adamantyl (meth)acrylate.

[0067] Implementation 6:

[0068] The fluorinated polymer according to any one of Embodiments 1 to 5, wherein

[0069] The amount of the first monomer (a) is 5 to 70 wt %, the amount of the second monomer (b) is 4 to 60 wt %, the amount of the third monomer (c) is 3 to 60 wt %, and the amount of the fourth monomer (d) is 3 to 60 wt % based on the fluorine-containing polymer.

[0070] Implementation 7:

[0071] The fluorinated polymer according to any one of Embodiments 1 to 6, wherein

[0072] The fluorine-containing polymer has a repeating unit formed of a monomer (e) other than the monomers (a), (b), (c) and (d), and the other monomer (e) is a halogenated olefin.

[0073] Implementation 8:

[0074] The fluorinated polymer according to embodiment 7, wherein the amount of other monomer (e) is 0 to 50% by weight.

[0075] Implementation 9:

[0076] A fluorine-containing composition comprising the following (1) and (2),

[0077] (1) the fluorinated polymer according to any one of embodiments 1 to 8,

[0078] (2) Liquid medium.

[0079] Implementation 10:

[0080] In the fluorine-containing composition as described in Embodiment 9, the liquid medium (2) is an organic solvent, or water, an organic solvent, or a mixture of water and an organic solvent.

[0081] Implementation 11:

[0082] The fluorinated composition according to embodiment 9 or 10, wherein the fluorinated composition is an aqueous dispersion in which a polymer is dispersed in water or a mixture of water and an organic solvent, and the fluorinated composition contains (3) a surfactant.

[0083] Implementation 12:

[0084] The fluorine-containing composition as described in any one of Embodiments 9 to 11, wherein the fluorine-containing composition is a water repellent, an oil repellent, an antifouling agent, a stain release agent, a peeling agent, or a mold release agent.

[0085] Implementation 13:

[0086] A treated object, comprising the fluorinated polymer according to any one of Embodiments 1 to 8 adhering thereto.

[0087] Effects of the Invention

[0088] According to the present invention, there can be obtained a fluorinated polymer and a fluorinated composition which impart excellent dynamic water repellency at a low concentration and excellent water repellency when used as an auxiliary agent. DETAILED DESCRIPTION

[0089] The fluorine-containing composition comprises the following (1) to (3),

[0090] (1) Fluorine-containing polymers,

[0091] (2) Liquid medium,

[0092] (3) Surfactant.

[0093] The fluorine-containing composition may also contain

[0094] (4) Curing agent.

[0095] The fluorine-containing composition may further contain (5) other components.

[0096] (1) Fluoropolymers

[0097] The fluorine-containing polymer has repeating units derived from a fluorine-containing monomer and a non-fluorine-containing monomer. The fluorine-containing monomer includes a first monomer (a), which is a fluorine-containing acrylic monomer having a chlorine atom at the α position, and a second monomer (b), which is a fluorine-containing acrylic monomer having a hydrogen atom or an organic group at the α position. The non-fluorine-containing monomer includes a third monomer (c), which is an acrylic monomer having a chain hydrocarbon group having 12 to 40 carbon atoms, and a fourth monomer (d), which is an acrylic monomer having a cyclic hydrocarbon group having 3 to 40 carbon atoms.

[0098] The fluorine-containing polymer may contain other monomers (e) in addition to the monomers (a), (b), (c) and (d). Other monomers (e) are halogenated olefins and the like.

[0099] (a) First monomer

[0100] The first monomer (a) is a fluorine-containing monomer.

[0101] The first monomer (a) is preferably a compound represented by the following formula:

[0102] CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf 11

[0103] [Wherein, X 11 is a halogen atom,

[0104] Y 11 is -O- or -NH-,

[0105] Z 11 is a direct bond or a divalent organic group,

[0106] R 11 is a fluoroalkyl group having 1 to 20 carbon atoms. ].

[0107] X 11 Preferably, it is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. 11 Representative examples are Cl, Br, I, F, X 11 Preferred is Cl.

[0108] The first monomer (a) is Y 11 A fluorinated acrylate monomer having -O-, or Y 11 A fluorinated acrylamide monomer containing -NH-. 11 Preferred is -O-.

[0109] Z 11 Examples of are direct bonds, aliphatic groups having 1 to 10 carbon atoms, aromatic groups having 6 to 18 carbon atoms, or cyclic aliphatic groups,

[0110] Formula - R 2 (R 1 )N-SO2-or-R 2 (R 1 )N-CO- represented by the group (wherein, R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a straight chain alkylene group or a branched alkylene group having 1 to 10 carbon atoms. ),

[0111] Formula - CH2CH(OR 3 )CH2-(Ar-O) p -(where R 3is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl), Ar is an arylene group having a substituent as required, and p represents 0 or 1. )

[0112] Formula - (CH2) r -Ar-(O) q -(wherein Ar is an arylene group which may optionally have a substituent, q is 0 or 1, and r is 0 to 10.), or a group represented by the formula -(CH2) m -SO2-(CH2) n - or -(CH2) m -S-(CH2) n - (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (especially one having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or SO2 group may be combined with Rf 11 Direct bonding of the base.

[0113] In monomer (a), Rf 11 The group is preferably a perfluoroalkyl group. 11 The number of carbon atoms in the group is preferably 1 to 12, for example 1 to 6, particularly preferably 4 to 6, and more preferably 6. 11 Examples of bases are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(C F2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8F 17 wait.

[0114] Specific examples of the monomer (a) include the following monomers, but are not limited to these.

[0115] CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf 11

[0116] CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf 11

[0117] CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf 11

[0118] CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf 11

[0119] CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf 11

[0120] CH2=C(-F)-C(=O)-NH-(CH2)2-Rf 11

[0121] CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf 11

[0122] CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf 11

[0123] CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf 11

[0124] CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf 11

[0125] CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf 11

[0126] CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf 11

[0127] CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf 11

[0128] CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf 11

[0129] CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf 11

[0130] CH2=C(-F)-C(=O)-NH-(CH2)3-Rf 11

[0131] CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf 11

[0132] CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf 11

[0133] CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf 11

[0134] CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf 11

[0135] (b) Second monomer

[0136] The second monomer (b) is a fluorine-containing monomer.

[0137] The second monomer (b) is preferably a compound represented by the following formula:

[0138] CH2=C(-X 12 )-C(=O)-Y 12 -Z 12 -Rf 12

[0139] [Wherein, X 12 A hydrogen atom or a monovalent organic group,

[0140] Y 12 is -O- or -NH-,

[0141] Z 12 is a direct bond or a divalent organic group,

[0142] R 12 is a fluoroalkyl group having 1 to 20 carbon atoms. ].

[0143] X 12 It is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 21 carbon atoms. 12 Representative examples of are hydrogen atom and methyl group. A hydrogen atom is particularly preferred.

[0144] The first monomer (a) is Y 12 Fluorinated acrylate monomers containing -O- or Y 12 A fluorinated acrylamide monomer containing -NH-. 12 Preferably it is O-.

[0145] Z 12 Examples of the compound include a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms, a 2 (R 1 )N-SO2- or formula-R 2 (R1 )N-CO- represented by the group (wherein, R 1 is an alkyl group having 1 to 10 carbon atoms, R 2 is a straight chain alkylene or branched alkylene having 1 to 10 carbon atoms. ) or a group of the formula -CH2CH(OR 3 )CH2-(Ar-O) p -(where R 3 is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl), Ar is an arylene group having a substituent as required, and p represents 0 or 1. ) or a group represented by the formula -(CH2) n -Ar-(O) q -(wherein Ar is an arylene group which may optionally have a substituent, and q is 0 or 1), -(CH2) m -SO2-(CH2) n - or -(CH2) m -S-(CH2) n - group (wherein m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (especially one having 1 to 4 carbon atoms, for example, 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or SO2 group may be combined with Rf 12 Direct bonding of the base.

[0146] In monomer (b), Rf 12 The group is preferably a perfluoroalkyl group. 12 The number of carbon atoms in the group is preferably 1 to 12, for example 1 to 6, particularly preferably 4 to 6, and more preferably 6. 12 Examples of bases are -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -CF2CF2CF2CF3, -CF2CF(CF3)2, -C(CF3)3, -(CF2)4CF3, -(C F2)2CF(CF3)2, -CF2C(CF3)3, -CF(CF3)CF2CF2CF3, -(CF2)5CF3, -(CF2)3CF(CF3)2, -(CF2)4CF(CF3)2, -C8F 17 wait.

[0147] Specific examples of the monomer (b) include the following monomers, but are not limited to these.

[0148] CH2=C(-H)-C(=O)-O-(CH2)2-Rf 12

[0149] CH2=C(-H)-C(=O)-O-C6H4-Rf 12

[0150] CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf 12

[0151] CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf 12

[0152] CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf 12

[0153] CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf 12

[0154] CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf 12

[0155] CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf 12

[0156] CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf 12

[0157] CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf 12

[0158] CH2=C(-H)-C(=O)-NH-(CH2)2-Rf 12

[0159] CH2=C(-CH3)-C(=O)-O-(CH2)2-Rf 12

[0160] CH2=C(-CH3)-C(=O)-O-C6H4-Rf 12

[0161] CH2=C(-CH3)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf 12

[0162] CH2=C(-CH3)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf 12

[0163] CH2=C(-CH3)-C(=O)-O-CH2CH(-OH)CH2-Rf 12

[0164] CH2=C(-CH3)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf 12

[0165] CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf 12

[0166] CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf 12

[0167] CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf 12

[0168] CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf 12

[0169] CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf 12

[0170] (c) The third monomer

[0171] The third monomer (c) is a monomer having no fluorine atom. The third monomer (c) is an acrylic monomer having a chain hydrocarbon group having 12 to 40 carbon atoms and one ethylenically unsaturated double bond.

[0172] The chain hydrocarbon group is preferably a straight-chain or branched hydrocarbon group. The chain hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. The lower limit of the number of carbon atoms of the chain hydrocarbon group is preferably 14, 16 or 18, and the upper limit is 30, 26 or 22. Specific examples of the chain hydrocarbon group are lauryl, hexadecyl, stearyl and behenyl.

[0173] The third monomer (c) is preferably a compound represented by the following formula:

[0174] CH2=C(-X 21 )-C(=O)-Y 21 -R 21

[0175] [Wherein, X 21 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0176] Y 21is -O- or -NH-,

[0177] R 21 It is a chain hydrocarbon group having 12 to 40 carbon atoms. ].

[0178] X 21 It may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom (particularly a chlorine atom, a bromine atom or an iodine atom), a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Preferably, it is a hydrogen atom, a methyl group or a chlorine atom.

[0179] The third monomer (c) may be Y 21 A long-chain acrylic ester monomer containing -O-, or Y 21 It is a long-chain acrylamide monomer with -NH-.

[0180] R 21 It is a straight-chain or branched hydrocarbon group, for example, an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. The number of carbon atoms in the chain hydrocarbon group is 14 to 30, for example, 16 to 26, particularly preferably 18 to 22.

[0181] Preferred specific examples of the third monomer (c) include lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, lauryl α-chloroacrylate, hexadecyl α-chloroacrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate, and behenyl α-chloroacrylate.

[0182] Other preferred specific examples of the third monomer (c) include lauryl (meth)acrylamide, hexadecyl (meth)acrylamide, stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0183] (d) Fourth monomer

[0184] The fourth monomer (d) is a monomer having no fluorine atom. The fourth monomer (d) is an acrylic monomer having a cyclic hydrocarbon group having 3 to 40 carbon atoms and one ethylenically unsaturated double bond.

[0185] The cyclic hydrocarbon group may be saturated or unsaturated, a monocyclic group, a polycyclic group, a bridged ring group, etc. The cyclic hydrocarbon group is preferably saturated. The number of carbon atoms in the cyclic hydrocarbon group is preferably 4 to 20 (for example, 6 to 15 or 6 to 10). Examples of the cyclic hydrocarbon group include cyclic aliphatic groups having 4 to 30 carbon atoms, especially 5 to 20 or 5 to 12 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and aromatic aliphatic groups having 7 to 25 or 7 to 20 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group may be 15 or less, for example, 10 or less. The carbon atoms in the ring of the cyclic hydrocarbon group may be directly bonded to the ester group in the (meth)acrylate group, or may be bonded via a hydrocarbon spacer. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

[0186] Specific examples of the cyclic hydrocarbon group include cyclohexyl, cyclopentyl, cyclobutyl, dicyclopentyl, dicyclopentenyl, adamantyl, isobornyl, naphthyl, bornyl, tricyclodecanyl, phenyl, biphenyl and triphenyl.

[0187] The fourth monomer (d) is preferably a compound represented by the following formula:

[0188] CH2=C(-X 22 )-C(=O)-Y 22 -R 22

[0189] [Wherein, X 22 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0190] Y 22 is -O- or -NH-,

[0191] R 22 It is a cyclic hydrocarbon group having 3 to 40 carbon atoms. ].

[0192] X 22 It may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom (particularly a chlorine atom, a bromine atom or an iodine atom), a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Preferably, it is a hydrogen atom, a methyl group or a chlorine atom.

[0193] The fourth monomer (c) may be Y 22 A long-chain acrylic ester monomer containing -O-, or Y 22 It is a long-chain acrylamide monomer with -NH-.

[0194] R 22 It is preferably a cyclic aliphatic group having 3 to 30 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 to 25 carbon atoms.

[0195] Specific examples of the fourth monomer (d) include cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0196] (e) Other monomers

[0197] The other monomer (e) is a monomer other than the monomers (a), (b), (c) and (d). The other monomer (e) is preferably a non-fluorine monomer.

[0198] Examples of other monomers (e) include halogenated olefins. Halogenated olefins do not contain fluorine atoms.

[0199] The halogenated olefin may be an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is a chlorinated olefin having 2 to 20 carbon atoms, and an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms is particularly preferred. Preferred specific examples of the halogenated olefin are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, and examples thereof include vinylidene chloride, vinylidene bromide, and vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred due to the improvement of water repellency (especially the durability of water repellency), and vinyl chloride is particularly preferred.

[0200] Examples of the additional monomer (e) include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, and vinyl alkyl ether.

[0201] In the fluorine-containing polymer, the amount of the fluorine-containing monomer (i.e., the total amount of the first monomer (a) and the second monomer (b)) may be 10% by weight or more, for example, 40% by weight or more, relative to the fluorine-containing polymer. The amount of the fluorine-containing monomer may be 95% by weight or less, for example, 80% by weight or less, or 75% by weight or less, or 70% by weight or less, relative to the fluorine-containing polymer.

[0202] In the fluorine-containing polymer, the weight ratio of the first monomer (a) to the second monomer (b) may be 5:95 to 95:5, 10:90 to 90:10, 15:85 to 85:15, or 20:80 to 80:20. Alternatively, the weight ratio of the first monomer (a) to the second monomer (b) may be 40:60 to 90:10, 50:50 to 85:15, 55:45 to 80:20, or 60:40 to 70:30.

[0203] In the fluorine-containing polymer, the weight ratio of the third monomer (a) to the fourth monomer (b) may be 5:95 to 95:5, 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0204] In the fluorinated polymer, relative to 100 parts by weight of the fluorinated monomer (the total amount of the first monomer (a) and the second monomer (b)),

[0205] The lower limit of the amount of the third monomer (c) is 1 part by weight, 5 parts by weight or 10 parts by weight, and the upper limit is 300 parts by weight, 200 parts by weight or 150 parts by weight.

[0206] The lower limit of the amount of the fourth monomer (d) is 1 part by weight, 5 parts by weight or 10 parts by weight, and the upper limit is 300 parts by weight, 200 parts by weight or 150 parts by weight.

[0207] The amount of other monomers (e) (eg, halogenated olefins) may have a lower limit of 0 parts by weight, 1 part by weight, or 2 parts by weight, and an upper limit of 100 parts by weight, 60 parts by weight, or 40 parts by weight.

[0208] Or, relative to the total of the monomers (ie, relative to the fluorinated polymer),

[0209] The lower limit of the amount of the first monomer (a) is 5 wt%, 10 wt%, 15 wt%, 20 wt% or 22 wt%, and the upper limit is 70 wt%, 60 wt%, 55 wt%, 50 wt% or 48 wt%,

[0210] The lower limit of the amount of the second monomer (b) is 4 wt%, 5 wt%, 8 wt%, 10 wt% or 11 wt%, and the upper limit is 60 wt%, 50 wt%, 40 wt%, 35 wt% or 30 wt%,

[0211] The lower limit of the amount of the third monomer (c) is 3 wt%, 5 wt%, 8 wt%, 9 wt% or 10 wt%, and the upper limit is 60 wt%, 50 wt%, 40 wt%, 30 wt% or 25 wt%,

[0212] The lower limit of the amount of the fourth monomer (d) is 3 wt%, 5 wt%, 8 wt%, 9 wt% or 10 wt%, and the upper limit is 60 wt%, 50 wt%, 40 wt%, 30 wt% or 25 wt%,

[0213] Regarding the amount of other monomers (e) (for example, the total amount of halogenated olefins and other monomers), the lower limit may be 0 wt%, 3 wt%, 8 wt%, 10 wt% or 15 wt%, and the upper limit may be 50 wt%, 40 wt%, 30 wt%, 25 wt% or 21 wt%. Regarding the amount of halogenated olefins, the lower limit is preferably 0 wt%, 2 wt%, 7 wt%, 10 wt% or 15 wt%, and the upper limit is preferably 50 wt%, 40 wt%, 30 wt%, 25 wt% or 21 wt%. By having such an amount, even if the concentration (i.e., amount) of the fluorinated polymer is low, the water repellency can be improved.

[0214] The weight average molecular weight of the non-fluorine polymer may have a lower limit of 1,000, 5,000 or 10,000, and an upper limit of 10,000,000, 8,000,000, 4,000,000, 800,000 or 400,000. The weight average molecular weight is a value determined by gel permeation chromatography in terms of polystyrene.

[0215] The lower limit of the amount of the fluorine-containing polymer (solid content) relative to the fluorine-containing composition may be 0.01 wt%, 0.1 wt%, 1 wt% or 5 wt%, and the upper limit may be 60 wt%, 40 wt%, 35 wt% or 30 wt%.

[0216] The fluorinated polymer may be in the form of a solution dissolved in an organic solvent, but preferably may be in the form of an aqueous dispersion.

[0217] In this specification, when "acrylate" or "acrylamide" is simply mentioned unless otherwise specified, it includes not only compounds in which the α-position is a hydrogen atom, but also compounds in which the α-position is substituted by other groups (e.g., a monovalent organic group containing a methyl group or a halogen atom). In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

[0218] (2) Liquid medium

[0219] The liquid medium can be an aqueous medium (water or a mixture of water and an organic solvent (an organic solvent that can be mixed with water)) or an organic solvent. The water-repellent and oil-repellent agent is generally a solution or a dispersion. The solution can be a solution in which a polymer is dissolved in an organic solvent or an aqueous medium. The dispersion is an aqueous dispersion in which a polymer is dispersed in an aqueous medium.

[0220] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, acetone, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropanol), aromatic solvents (e.g., toluene and xylene), petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene), and halogenated alkyls (e.g., halogenated alkyls having 1 to 40 carbon atoms, specifically, chloroform).

[0221] The liquid medium may be water alone, an organic solvent alone, or a mixture of water and an organic solvent (miscible with water). The amount of the organic solvent may be 30% by weight or less, for example 10% by weight or less (preferably 0.1% by weight or more), relative to the liquid medium. The liquid medium is preferably water alone.

[0222] The lower limit of the amount of the liquid medium may be 30 wt %, 50 wt % or 70 wt % and the upper limit may be 99.5 wt %, 99 wt % or 95 wt % relative to the fluorine-containing composition.

[0223] The aqueous medium can be added after the fluoropolymer is manufactured by polymerization. For example, the monomer is polymerized in the presence of an organic solvent, water is added after the fluoropolymer is manufactured, and the organic solvent is distilled off. The organic solvent may not be distilled off. The surfactant may be added before or after the polymerization, or may not be added. Even without adding a surfactant, an aqueous dispersion in which the fluoropolymer is well dispersed in the aqueous medium can be obtained.

[0224] (3) Surfactants

[0225] When the fluorine-containing composition is an aqueous dispersion, it may contain a surfactant. The surfactant contains at least one of a nonionic surfactant, a cationic surfactant and an anionic surfactant. Furthermore, the surfactant may contain an amphoteric surfactant. In addition, the surfactant may not be contained.

[0226] When the fluorine-containing composition is an aqueous dispersion, it usually contains a surfactant. When the fluorine-containing composition is an aqueous solution, it usually does not contain a surfactant.

[0227] The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The carbon number of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100.

[0228] The nonionic surfactant may be an oxyalkylene adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an oxyalkylene adduct of acetylene glycol, etc. Among these, it is preferred that the structure of the alkylene oxide addition part and the polyalkylene glycol part is polyethylene oxide (POE) or polypropylene oxide (POP) or a POE / POP copolymer (which may be a random copolymer or a block copolymer).

[0229] In addition, due to environmental issues (biodegradability, environmental hormones, etc.), the nonionic surfactant preferably has a structure without an aromatic group.

[0230] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an ethylene oxide addition type ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and include amine salt-type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, quaternary ammonium salt-type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0231] Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0232] Examples of anionic surfactants include fatty acid salts (the carbon number of the fatty acid is, for example, 8 to 30), sulfonates (for example, alkylsulfonic acids and alkylbenzenesulfonates (the carbon number of the alkyl group is, for example, 8 to 30)), and sulfate ester salts (for example, alkyl sulfate ester salts (the carbon number of the alkyl group is, for example, 8 to 30).

[0233] Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium 0-polyoxyethylene nonylphenyl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, sodium cocoyl sarcosinate, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, and the like.

[0234] Examples of the amphoteric surfactant include alanines, imidazolinium betaines, amidobetaines, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amide propyl dimethylaminoacetic acid betaine.

[0235] One or a combination of two or more of a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant may be used.

[0236] The surfactant is preferably an anionic surfactant and / or a nonionic surfactant. A combination of an anionic surfactant and a nonionic surfactant is preferred.

[0237] In the present invention, even when a surfactant is not used, a dispersion liquid of the fluorinated polymer, particularly an aqueous dispersion liquid, can be formed.

[0238] The amount of the surfactant may be 0.1 to 50 parts by weight, for example 1 to 30 parts by weight, based on 100 parts by weight of the fluorine-containing polymer (or the total of the monomers).

[0239] [Method for producing fluorinated polymer]

[0240] The fluorine-containing polymer of the present invention can be produced by any conventional polymerization method, and the polymerization reaction conditions can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

[0241] When solution polymerization is carried out, a method is adopted in which the monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the monomer is heated and stirred at a temperature of 30 to 120° C. for 30 minutes to 48 hours, for example, for 3 to 24 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, relative to 100 parts by weight of the monomer.

[0242] The organic solvent is a substance that is inactive to the monomer but can dissolve it, and may be, for example, an ester (e.g., an ester having 2 to 30 carbon atoms, specifically, ethyl acetate and butyl acetate), a ketone (e.g., a ketone having 2 to 30 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), or an alcohol (e.g., an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.

[0243] When conducting emulsion polymerization, the monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the monomer is stirred at a temperature of 50 to 80° C. for 30 minutes to 48 hours, for example, 3 to 24 hours to polymerize. The polymerization initiator can use a water-soluble initiator such as benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyramidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or an oil-soluble initiator such as azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, dodecyl peroxide, isopropylbenzene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxycarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

[0244] In order to obtain an aqueous polymer dispersion with excellent shelf stability, it is preferred to use an emulsifying device such as a high-pressure homogenizer and an ultrasonic homogenizer that can apply strong crushing energy to form the monomer in water for polymerization. In addition, as an emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are completely incompatible, it is preferred to add a compatibilizer that makes these monomers fully compatible, such as a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, the emulsification and copolymerization properties can be improved.

[0245] Examples of water-soluble organic solvents include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, which can be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of water. In addition, examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, which can be used in an amount of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0246] In the polymerization, a chain transfer agent may also be used. The molecular weight of the polymer can be changed by the amount of the chain transfer agent used. Examples of chain transfer agents include mercapto group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly (e.g., alkyl mercaptan (having 1 to 30 carbon atoms)), sodium hypophosphite, sodium bisulfite, and other inorganic salts. The amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, relative to 100 parts by weight of the total amount of the monomers.

[0247] The fluorine-containing polymer is preferably produced by emulsion polymerization or solution polymerization.

[0248] It is preferred that after the fluorine-containing polymer is produced by polymerization, water (or an aqueous medium) is added to disperse the fluorine-containing polymer in water.

[0249] Water (or aqueous medium) can be added after the fluoropolymer is manufactured by polymerization. For example, after the fluoropolymer is manufactured by polymerization of monomers in the presence of an organic solvent, water is added to the polymer mixture, and the organic solvent is distilled off to disperse the fluoropolymer in water. The organic solvent may also not be distilled off. The surfactant may be added before or after the polymerization, or it may not be added. In the case of not adding a surfactant, a good aqueous dispersion can also be obtained.

[0250] The fluorine-containing composition may contain (4) a curing agent (an active hydrogen-reactive compound or a compound containing active hydrogen). The curing agent (4) is usually added after the fluorine-containing polymer is produced.

[0251] (4) Curing agent

[0252] In order to cure the fluorine-containing polymer well, the fluorine-containing composition may contain a curing agent (crosslinking agent). Since the non-fluorine crosslinkable (meth)acrylate or (meth)acrylamide monomer is a monomer containing active hydrogen or a monomer containing an active hydrogen reactive group, the fluorine-containing polymer has active hydrogen or an active hydrogen reactive group. In order to react with the active hydrogen or active hydrogen reactive group of the fluorine-containing polymer, the curing agent is an active hydrogen reactive compound or a compound containing active hydrogen.

[0253] Examples of the active hydrogen-reactive compound include polyisocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds.

[0254] Examples of the compound containing active hydrogen include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a keto group-containing compound, a hydrazide compound, and a melamine compound.

[0255] The amount of the curing agent is 100 parts by weight or less, for example, 0.01 to 30 parts by weight, based on 100 parts by weight of the fluorine-containing polymer.

[0256] The curing agent is preferably a polyisocyanate compound.

[0257] The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

[0258] Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates of 2,6-diisocyanatomethylhexanoate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0259] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates, etc. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane.

[0260] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene.

[0261] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-toluene diisocyanate or a mixture thereof, triphenylmethane-4,4',4"-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0262] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biuret, allophanate, carbodiimide, uretdione, uretonimine, isocyanurate, and iminooxadiazinedione.

[0263] These polyisocyanates may be used alone or in combination of two or more.

[0264] As the polyisocyanate compound, it is preferred to use a compound in which the isocyanate group of the polyisocyanate compound is blocked by a blocking agent, i.e., a blocked polyisocyanate compound (blocked isocyanate). It is preferred to use a blocked polyisocyanate compound for reasons such as being relatively stable in aqueous solution and being able to be used in the same liquid (e.g., aqueous solution) as the fluorine-containing composition.

[0265] The blocking agent is a substance used to block free isocyanate groups. The blocked polyisocyanate compound is heated to 100° C. or higher, for example, 130° C. or higher, to regenerate the isocyanate groups and to react easily with hydroxyl groups. Examples of the blocking agent include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and the like.

[0266] The polyisocyanate compound can be used alone or in combination of two or more.

[0267] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether.

[0268] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include chloromethyl polystyrene and the like.

[0269] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly)acrylic acid, (poly)methacrylic acid, and the like.

[0270] The ketone group-containing compound is a compound having a ketone group. Examples of the ketone group-containing compound include (poly) diacetone acrylamide, diacetone alcohol, and the like.

[0271] The hydrazide compound is a compound having a hydrazide group. Examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide and the like.

[0272] Examples of the melamine compound include melamine resin, methyl etherified melamine resin and the like.

[0273] (5) Other ingredients

[0274] The fluorine-containing composition may contain other components (5) in addition to the above-mentioned components (1) to (4).

[0275] Typically, the other ingredients are added after the fluoropolymer is made (5).

[0276] The lower limit of the amount of other components relative to 100 parts by weight of the fluorine-containing polymer may be 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 5 parts by weight or 10 parts by weight, and the upper limit may be 1000 parts by weight, 500 parts by weight, 100 parts by weight, 50 parts by weight or 20 parts by weight.

[0277] Examples of other components (5) include water- and / or oil-repellents, anti-slip agents, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, penetrants, reactive silicone components, silicone resins, etc. These may be used alone or in combination of two or more. In addition to the above components, other components may include a texture regulator, a softener, an antibacterial agent, a flame retardant, a paint fixative, an anti-wrinkle agent, a drying speed regulator, a cross-linking agent, a film-forming aid, a volume extender, an antifreeze agent, a viscosity regulator, an ultraviolet absorber, an antioxidant, a pH regulator, an insect repellent, a defoamer, an anti-shrinkage agent, an anti-wrinkle agent for washing, a shape retaining agent, a droop retaining agent, an ironing property improving agent, a whitening agent, a whitening agent, a fabric softening clay, an anti-migration agent such as polyvinyl pyrrolidone, a polymer dispersant, a dirt release agent, a scum dispersant, 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal manufactured by Ciba Specialty Chemicals) CBS-X) and other fluorescent whitening agents, dye fixing agents, fading prevention agents such as 1,4-bis(3-aminopropyl)piperazine, detergents, enzymes such as cellulase, amylase, protease, lipase, gelatinase as fiber surface modifiers, foam inhibitors, silk protein powders that can impart texture-functions to silk such as moisture absorption and release, surface modified products thereof, emulsified dispersions, specifically, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Uemo), SILKGEN G Soluble S (Ichimaru PHARCOS), nonionic polymer compounds composed of polyoxyalkylene units composed of terephthalate alkyl esters and / or metaphthalate alkyl esters, for example, FR627 manufactured by Huying Chemical Industry, SRC-1 manufactured by Clarion Japan, and other pollution prevention agents can be combined. These can be used alone or in combination of two or more.

[0278] (Water and / or oil repellent)

[0279] Examples of water-repellent and / or oil-repellent agents include saturated or unsaturated hydrocarbon compounds or silicone compounds. The water-repellent and / or oil-repellent agent may be non-fluorine. The saturated or unsaturated hydrocarbon compound is preferably a saturated hydrocarbon. The number of carbon atoms in the saturated or unsaturated hydrocarbon compound may be 15 or more, preferably 20 to 300, for example 25 to 100. Specific examples of saturated or unsaturated hydrocarbon compounds include paraffin wax and the like. Examples of silicone compounds include silicones, siloxane-containing acrylic polymers and the like. These may be used alone or in combination of two or more.

[0280] (Anti-slip agent)

[0281] Examples of anti-slip agents include polyurethane resins, acrylic resins, silicones (reactive silicones, silicone resins, etc.), combined resins thereof, aluminum compounds (e.g., aluminum oxide), silicon compounds (e.g., silicon dioxide), inorganic particles such as titanium compounds (which may be subjected to a hydrophobic surface treatment), etc. These may be used alone or in combination of two or more.

[0282] (Antistatic Agent)

[0283] Examples of antistatic agents include cationic antistatic agents with cationic functional groups such as quaternary ammonium salts, pyridinium salts, primary amino groups, secondary amine groups, and tertiary amine groups; anionic antistatic agents with anionic functional groups such as sulfonates, sulfates, phosphonates, and phosphates; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and their derivatives, nonionic antistatic agents such as amino alcohols and their derivatives, glycerol and their derivatives, polyethylene glycol and their derivatives, etc. It can also be an ion conductive polymer obtained by polymerizing or copolymerizing these monomers with cationic, anionic, and zwitterionic ion conductive groups. These can be used alone or in combination of two or more.

[0284] (preservative)

[0285] Preservatives can be mainly used to enhance the antiseptic power and bactericidal power, and to maintain the antiseptic property during long-term storage. Examples of preservatives include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, etc. Relative to the total weight of the fluorine-containing composition, the content of the preservative is preferably 0.0001 to 1 weight percent. When the content of the preservative is above the lower limit of the above range, the effect of adding the preservative can be fully obtained, and when it is below the upper limit, the storage stability of the fluorine-containing composition can be improved.

[0286] (Ultraviolet light absorber)

[0287] The ultraviolet absorber is a drug having an ultraviolet protection effect, and is a component that absorbs ultraviolet rays and converts them into infrared rays or visible light, etc. Examples of the ultraviolet absorber include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, 4-tert-butyl-4'-methoxybenzoylmethane, etc.

[0288] (Antibacterial Agent)

[0289] The antimicrobial agent is a component that has the effect of inhibiting the proliferation of bacteria on the fiber and also inhibiting the generation of unpleasant odors from the decomposition products of microorganisms. Examples of the antimicrobial agent include cationic fungicides such as quaternary ammonium salts (but excluding component (A)), bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanide hydrochloride, 8-oxyquinoline, polylysine, and the like.

[0290] (Deodorant)

[0291] Examples of the deodorant include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyl dimethylamine oxide, and aminocarboxylic acid metal complexes (zinc complex of trisodium methylglycine diacetate described in International Patent Publication No. 2012 / 090580).

[0292] (spices)

[0293] The fragrance is not particularly limited, and the list of fragrance raw materials that can be used can be referred to various documents, such as "Perfume and Flavor Chemicals", Vol. I and II, Steffen Arctander, Allured Pub. Co. (1994), "Synthetic Fragrance Chemistry and Product Knowledge", written by Motokazu Indo, Chemical Industry Daily (1996), "Perfume and Flavor Materials of Natural Origin", Steffen Arctander, Allured Pub. Co. (1994), "Encyclopedia of Fragrance", edited by Japan Fragrance Association, Asakura Bookstore (1989) and "Perfumery Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oils and Floral Compounds In Perfumery", Danute Lajaujis Anonis, Allured Pub. Co. (1993), etc., which are respectively cited in the present specification and made a part of the disclosure.

[0294] (Penetrant)

[0295] There is no particular limitation on the penetrant, and alcohol, anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, etc. can be cited as the penetrant, and specifically alcohols with alkyl groups having carbon atoms of 1 to 10, polyoxyethylene alkyl ethers, etc. can be cited. The penetrant can be used alone or in combination of two or more. In the hydrophobic substrate treatment agent composition (100 wt%), the concentration of the penetrant is preferably 0.01 to 1.0 wt%. From the viewpoint of both permeability and water repellency and alcohol repellency for the hydrophobic substrate, 0.1 to 0.5 wt% is more preferred.

[0296] (Reactive silicone component)

[0297] From the viewpoint of improving the function, the fluorine-containing composition may contain a reactive silicone component. Among the reactive silicone components, polysiloxanes having a side chain, a single end, two ends, a side chain and two ends having a reactive group can be cited, but from the viewpoint of making the slip excellent and the antifouling property (SR property) excellent, polysiloxanes having a reactive group in the side chain and / or at both ends are preferably used. As the reactive silicone component, as long as it has a reactive group in the molecule, it is not particularly limited, and for example, amino-modified silicone, epoxy-modified silicone, carboxyl-modified silicone, methyl hydrogen silicone, etc. can be cited.

[0298] As amino-modified silicone, amino-modified silicone having a structure in which an amino group is bonded to an organic group directly linked to a silicon atom can be cited. The organic group can be an alkylene group or a divalent aromatic group. As an alkylene group, an alkylene group having 2 or more carbon atoms is preferred. As a divalent aromatic group, an aromatic group having 6 or more carbon atoms is preferred. As an amino group, a primary amino group, a secondary amino group, and a tertiary amino group can be used. As an organic group bonded to an amino group, the following groups can be exemplified. 2-aminoethyl, N-methyl-2-aminoethyl, N,N-dimethyl-2-aminoethyl, N-ethyl-2-aminoethyl, N,N-diethyl-2-aminoethyl, N,N-methylethyl-2-aminoethyl, 3-aminopropyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N-ethyl-3-aminopropyl, N,N-diethyl-3-aminopropyl, N,N-methylethyl-3-aminopropyl. These functional groups can be located at the side chains of the polysiloxane or at the ends.

[0299] As epoxy-modified silicone, there can be cited substances having a structure in which an epoxy group is bonded to an organic group directly linked to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. As such a form, a form in which a glycidyl ether is bonded between the above-mentioned organic groups is usually used. As such a functional group, 3-glycidoxypropyl and 2-glycidoxyethyl can be exemplified. These functional groups can be located in the side chain of the polysiloxane or at the end.

[0300] As carboxyl modified silicone, there can be cited substances having a structure in which a carboxyl group is bonded to an organic group directly linked to a silicon atom. The organic group may be an alkylene group or a divalent aromatic group. As the alkylene group, an alkylene group having 2 or more carbon atoms is preferred. As the divalent aromatic group, an aromatic group having 6 or more carbon atoms is preferred. As such functional groups, 3-carboxypropyl and 2-carboxyethyl can be exemplified. These functional groups may be located in the side chain of the polysiloxane or at the end.

[0301] Methyl hydrogen silicone refers to a compound in which a part of the side chain of a polydiorganosiloxane is substituted with hydrogen and a hydrogen atom is directly linked to a silicon atom. In the use of methyl hydrogen silicone, a catalyst may also be used to improve reactivity. For example, catalysts of zinc, tin, manganese, cobalt, iron and amine series can be used. As these catalysts, organic acid metal salts are preferably used, and as organic acids, fatty acids are preferably used. From the viewpoint of safety, zinc stearate and the like can be used. It is easy to exert the effect when 10% to 40% of the catalyst is used relative to methyl hydrogen silicone, so it is preferred. Regarding amino-modified, epoxy-modified silicones, carboxyl-modified silicones and methyl hydrogen silicones, two or more kinds may also be mixed. These are all silicones having reactive groups, preferably silicones having film-forming properties. Film-forming properties refer to the property of forming a solid film instead of becoming oily or gel-like after the silicone is attached to the fiber surface in an emulsion state.

[0302] (Silicone resin)

[0303] From the viewpoint of improving the function, the fluorine-containing composition may contain a silicone resin. The silicone resin is a resin selected from R3SiO 1 / 2 Unit (M unit), RSiO 3 / 2 unit (T unit) and SiO 4 / 2 The silicone resin (B) contains at least one silicone resin having at least one unit (Q unit), wherein R is a linear or branched monovalent alkyl group having 1 to 18 carbon atoms, and does not include a silicone resin consisting only of M units and Q units. 2 / 2 Unit (D unit) is preferred from the viewpoint of exerting the effects of the present application.

[0304] The silicone resin is preferably in a sol state. Examples of R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, hexadecyl, stearyl, etc. However, in view of the stability of the silicone resin (B) in a sol state, the availability of raw materials, and the price, R is preferably a methyl group, and in particular, more than 90% of all R groups are preferably methyl groups. It should be noted that R groups of different types may be used simultaneously.

[0305] Silicone resin contains R2SiO2 / 2 If the silicone resin is composed of only Q units (D units), the low slip properties of the water repellent may be impaired. In addition, a silicone resin composed of only Q units may inhibit the water repellency of the water repellent.

[0306] The structure of the silicone resin may be exemplified by a silicone resin consisting of (i) M units and Q units, (ii) M units, T units and Q units, (iii) M units and T units, (iv) T units and Q units, and (v) T units alone. Preferably, it may be a silicone resin consisting of (i) M units and Q units and a silicone resin consisting of (v) T units alone. The molar ratio (M / Q) of the M units to the Q units in the silicone resin consisting of (i) M units and Q units is preferably M / Q=0.6 to 1.3, and more preferably M / Q=0.8 to 1.1. It should be noted that two or more of these silicone resins may be used simultaneously.

[0307] In addition, the silicone resin (B) may contain a structural unit containing a hydroxyl group bonded to a silicon atom. Specifically, (HO)RSiO 2 / 2 Unit, (HO)2RSiO 1 / 2 Unit, (HO)SiO 3 / 2 Unit, (HO)2SiO 2 / 2 Unit, (HO)3SiO 1 / 2 In the unit, part of the hydroxyl groups is an alkoxy group represented by an RO group.

[0308] The sol containing silicone resin can be produced by the following method as described in Patent 3852921, namely, a method of uniformly dispersing and polymerizing an organodisiloxane, a tetraalkoxysilane, and a partially hydrolyzed condensate thereof in water containing a surfactant, or a method of hydrolyzing the following silane compound in water.

[0309] The manufacturing method of hydrolyzing a silane compound in water is described in detail. As the raw material used for manufacturing, the type of hydrolyzable group is chlorine or alkoxy, and it can contain 1, 3 or 4 hydrolyzable groups. As long as it is a silane compound with an alkyl group that meets the above conditions, it can be used. Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrichlorosilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrichlorosilane, Butyltrimethoxysilane, Butyltriethoxysilane, Isobutyltrichlorosilane, Isobutyltrimethoxysilane, Isobutyltriethoxysilane, Hexyltrichlorosilane, Hexyltrimethoxysilane, Hexyltriethoxysilane, 2-Ethylhexyltrichlorosilane, 2-Ethylhexyltrimethoxysilane, 2-Ethylhexyltriethoxysilane, Decyltrichlorosilane, Decyltrimethoxysilane, Decyltriethoxysilane, Hexadecyltrichlorosilane, Hexadecyltrimethoxysilane, Hexadecyltriethoxysilane, Hard Aliphatic trichlorosilane, stearyl trimethoxysilane, stearyl triethoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropoxysilane, dimethylethylchlorosilane, dimethylethylmethoxysilane, dimethylethylethoxysilane, dimethylpropylchlorosilane, dimethylpropylmethoxysilane, dimethylpropylethoxysilane, dimethylisopropylchlorosilane, dimethylisopropylmethoxysilane, dimethylisopropylethoxysilane, dimethylhexylchlorosilane Silane, dimethylhexylmethoxysilane, dimethylhexylethoxysilane, dimethyldecylchlorosilane, dimethyldecylmethoxysilane, dimethyldecylethoxysilane, dimethylhexadecylchlorosilane, dimethylhexadecylmethoxysilane, dimethylhexadecylethoxysilane, dimethylstearylchlorosilane, dimethylstearylmethoxysilane, dimethylstearylethoxysilane and these partial hydrolyzates are used as silane compounds, but the silane compounds that can be used are not limited to these. From the perspective of operability, the ease of distillation removal of by-products and the easy availability of raw materials, it is more preferred to use methoxysilane or ethoxysilane. It is also possible to use one or a mixture of two or more of these silane compounds.

[0310] As a method for hydrolyzing a silane compound in water, a generally known conventional method can be used, that is, a method of performing a hydrolysis reaction while dropping a silane compound into water, or a method of performing a hydrolysis reaction after mixing water and a silane compound.

[0311] When implementing the hydrolysis reaction, a hydrolysis catalyst can also be used. As a hydrolysis catalyst, a conventionally known catalyst can be used, and an acidic or alkaline catalyst can be used. In the case of an acidic catalyst, solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins are preferred. In the case of an alkaline catalyst, alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate, alkali metal siliconates such as sodium siliconates and potassium siliconates, amines such as triethylamine, diethylamine, and aniline, and ammonia water can be used. The amount of the catalyst is preferably able to adjust its addition amount in a manner that the pH of the aqueous solution becomes 2 to 7 and 7 to 12. In addition, after the reaction is completed, a neutralizing agent that neutralizes the acidic or alkaline catalyst can be added as needed.

[0312] A surfactant for dispersing the silane compound and the hydrolysis reaction product in water can also be added to the aqueous solution. The surfactant is not particularly limited, and can be used, for example, anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, cationic surfactants such as quaternary ammonium salts, alkylamine acetates, amphoteric surfactants such as alkyl betaines and alkyl imidazolines, etc., which can be used alone or in combination with two or more. In addition, as a surfactant, a substance showing acidity or alkalinity can also be used as a hydrolysis catalyst. The amount added when adding a surfactant is not particularly limited, and is preferably 1 to 50 parts by weight relative to 100 parts by weight of the silane compound. When less than 1 part by weight, the effect of adding a surfactant cannot be fully obtained, and when more than 50 parts by weight, the water repellency of the water repellent may be impaired.

[0313] A hydrolysis catalyst and a surfactant may be added to a mixture of water and a silane compound as required, and a hydrolysis reaction may be carried out at 0 to 90°C for 10 minutes to 24 hours. Afterwards, a neutralization reaction may be carried out as required to obtain a silicone resin. In addition, alcohols and neutralization salts produced as by-products of the hydrolysis reaction may be removed by vacuum distillation and filtration. Various additives may be added to the silicone resin. For example, a preservative, a tackifier, etc. may be added according to the purpose.

[0314] The fluorine-containing composition of the present invention may be in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The fluorine-containing composition may contain a polymer (active ingredient) and a medium (particularly a liquid medium, such as an organic solvent and / or water). For example, the amount of the medium is 5 to 99.9% by weight, and particularly 10 to 80% by weight, relative to the fluorine-containing composition.

[0315] The concentration of the polymer in the fluorine-containing composition may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

[0316] The fluorine-containing composition of the present invention can be applied to the treated object by existing known methods. Usually, the fluorine-containing composition is dispersed in an organic solvent or water for dilution, and it is attached to the surface of the treated object by known methods such as dip coating, spray coating, foam coating, and then dried. In addition, if necessary, a suitable cross-linking agent (curing agent) can also be used together for curing. Moreover, additives such as insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, coating fixatives, and wrinkle-proofing agents can also be added and used in the fluorine-containing composition of the present invention. The concentration of the polymer in the treatment liquid when in contact with the fiber product is 0.01 to 10 weight % (especially in the case of dip coating), for example, it can be 0.05 to 10 weight %.

[0317] As the treated object treated by the fluorine-containing composition of the present invention (e.g., water-repellent and oil-repellent agent), fiber products, stone materials, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coatings, and gypsum, etc., can be cited. As fiber products, various examples can be cited. For example, natural fibers of animals and plants such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate fibers, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof can be cited.

[0318] The fiber product may be in any form such as fiber, cloth, etc.

[0319] The fluorine-containing composition of the present invention can also be used as an internal mold release agent or an external mold release agent.

[0320] The polymer can be applied to the fiber product by any of the known methods of treating the fiber product (such as cloth) with a liquid. The fiber product can be immersed in the solution, or the solution can be attached or sprayed on the fiber product. In order to make the treated fiber product show water repellency and oil repellency, it is preferably dried and cured by heating. The heating temperature is, for example, 100°C to 200°C, and can be 100°C to 170°C or 100°C to 120°C. In the present invention, good performance can be obtained even with low temperature heating (for example, 100°C to 140°C). The heating time in the present invention can be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0321] Alternatively, the polymer may be applied to the fiber article by a washing process, for example, by washing or in a dry washing process or the like.

[0322] The treated fiber products are typically cloth, including woven fabrics (woven fabrics), knitted fabrics (woven fabrics) and nonwoven fabrics, cloth in the form of clothing and carpets, etc., but can also be fibers or silk threads or intermediate fiber products (such as carded cotton or roving, etc.). The fluorine-containing composition of the present invention is particularly effective in making synthetic fibers hydrophobic and water-repellent. In addition, the method of the present invention generally makes the fiber products hydrophobic and water-repellent.

[0323] Examples of fibers constituting the fiber products include natural fibers, synthetic fibers, semisynthetic fibers, regenerated fibers, and inorganic fibers. The fibers may be used alone or in combination of two or more.

[0324] Examples of natural fibers include cellulose fibers such as cotton, flax, wood pulp, chitin, chitosan, wool, and silk. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressure groundwood pulp (PGW), and thermomechanical pulp (TMP), chemical pulps such as high-content unbleached coniferous kraft pulp (HNKP; N material), coniferous bleached kraft pulp (NBKP; N material, NB material), broadleaf unbleached kraft pulp (LUKP; L material), and broadleaf bleached kraft pulp (LBKP, L material), and waste paper pulps such as de-inked (DIP) and waste paper pulp (WP) or semi-chemical pulp (CP).

[0325] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymer polyesters; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; polyvinyl alcohol, polyurethane, and polyvinyl chloride.

[0326] Examples of semi-synthetic fibers are acetate, triacetate.

[0327] Examples of regenerated fibers are rayon, cupro, polynosic, lyocell, tencel.

[0328] Examples of inorganic fibers include glass fibers and carbon fibers.

[0329] Alternatively, the fiber product may be leather. In order to render the leather hydrophobic and oleophobic, the manufacturing polymer may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, for example during wet processing of the leather or during final treatment of the leather.

[0330] Alternatively, the fibrous product may be paper. The manufacturing polymer may be applied to a preformed paper or it may be applied at various stages of papermaking, for example during drying of the paper.

[0331] "Treatment" means applying a treatment agent (fluorine-containing composition or its dilution) to the object to be treated by dipping, spraying, coating, etc. By the treatment, the polymer as an active ingredient of the treatment agent penetrates into the object to be treated and / or adheres to the surface of the object to be treated.

[0332] The present invention will be described in detail below with reference to the following examples, but the present invention is not limited to these examples.

[0333] Hereinafter, parts, % or ratios represent parts by weight, % by weight or ratio by weight unless otherwise specified.

[0334] The test process is as follows.

[0335] Spray water repellency test

[0336] The spray water repellency test was conducted in accordance with JIS-L-1092. The spray water repellency test was indicated by a water repellency No. (shown in Table 1 described later).

[0337] Use a glass funnel with a volume of at least 250 ml and a nozzle capable of spraying 250 ml of water for 20 to 30 seconds. The test piece holder is a metal holder with a diameter of 15 cm. Prepare 3 test piece sheets of approximately 20 cm × 20 cm in size and fix the sheets to the test piece holder so that the sheets have no wrinkles. Place the center of the spray at the center of the sheet. Place room temperature water (250 mL) in the glass funnel and spray the test piece sheet (for 25 to 30 seconds). Remove the holder from the table, grasp one end of the holder, and tap the opposite end gently on a hard substance with the front surface as the lower side. Rotate the holder further 180° and repeat the same procedure to remove excess water drops. In order to evaluate the water repellency in the order of 0, 50, 70, 80, 90 and 100 in the order of poor to excellent, compare the wet test piece with the wet comparison standard. The result is obtained by averaging the 3 measurements.

[0338] [Table 1]

[0339] Water repellency No. status

[0340]

[0341] Production Example 1

[0342] Put CF3CF2-(CF2CF2) into a 1000mL autoclave. n-CH2CH2OCOC(Cl)=CH2(n=2.0)(13FClA)44g, CF3CF2-(CF2CF2) n -CH2CH2OCOCH=CH2(n=2.0)(13FA) 12g, isobornyl methacrylate (IBMA) 20g, stearyl acrylate (StA) 4g, pure water 400g, water-soluble glycol solvent 56g, alkyl dimethyl ammonium chloride 1.56g, polyoxyethylene alkyl ether 16.1g, were emulsified and dispersed at 60°C for 15 minutes using ultrasound under stirring. After nitrogen substitution in the flask, 20g of vinyl chloride (VCM) was pressed and filled, and then 0.4g of azo-containing water-soluble initiator was added, and the reaction was carried out at 60°C for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is basically the same as that of the monomers fed.

[0343] Production Examples 1 to 6 and Comparative Production Examples 1 to 7

[0344] A polymer dispersion was obtained by repeating the same operation as in Preparation Example 1 except that the monomers shown in Table 2 were used. The composition of the polymer was substantially the same as that of the monomers fed.

[0345] Example 1

[0346] The aqueous liquid prepared in Preparation Example 1 was diluted with pure water to a fluoropolymer concentration of 30% solid content, and then further diluted with water to a ratio of 5% dilution to prepare a 5.00% test solution (100 g). Ten pieces of PET (PolyEthylene Terephthalate) woven fabric (500 mm × 200 mm) and Nylon woven fabric (500 mm × 200 mm) were continuously immersed in the test solution, passed through a calender, and treated at 170°C for 1 minute using a pin tenter. Similarly, after the fluoropolymer concentration was diluted to 30% solid content, it was further diluted with water to a ratio of 1% dilution, and a PP (Poly Propylene) nonwoven fabric (500 mm × 200 mm) was immersed in the test solution, passed through a calender, and treated at 135°C for 30 seconds using a pin tenter. Afterwards, the PET fabric and Nylon fabric were subjected to spray water repellency test, oil repellency test and washing durability test, respectively, and the PP nonwoven fabric was subjected to water repellency test (spray water repellency test, water repellency test (IPA), IPR test, water pressure resistance test). The results are shown in Table 2.

[0347] Examples 2 to 6 and Comparative Preparation Examples 1 to 7

[0348] The same operation as in Example 1 was repeated except that the polymer dispersions obtained in Production Examples 2 to 6 and Comparative Production Examples 1 to 7 were used instead of the polymer dispersion obtained in Production Example 1. The results are shown in Table 2.

[0349] [Table 2]

[0350]

[0351] Industrial Applicability

[0352] The fluorine-containing composition of the present invention can be used as a surface treatment agent, a water repellent, an oil repellent, an antifouling agent, a dirt-releasing agent, a peeling agent or a mold release agent.

Claims

1. A fluorine-containing polymer, characterized in that: having a repeating unit formed of the following first monomer (a), second monomer (b), third monomer (c) and fourth monomer (d), a first monomer (a) which is a fluorine-containing acrylic monomer having a chlorine atom at the α-position, The second monomer (b) is a fluorine-containing acrylic monomer having a hydrogen atom or an organic group at the α position, The third monomer (c) is an acrylic monomer having a chain hydrocarbon group having 12 to 40 carbon atoms, The fourth monomer (d) is an acrylic monomer having a cyclic hydrocarbon group having 3 to 40 carbon atoms.

2. The fluorinated polymer according to claim 1, characterized in that: The weight ratio of the third monomer (a) to the fourth monomer (b) is 5:95 to 95:

5.

3. The fluorinated polymer according to claim 1 or 2, characterized in that: The first monomer (a) is a compound represented by the following formula: CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf 11 Where, X 11 is a halogen atom, Y 11 is -O- or -NH-, Z 11 is a direct bond or a divalent organic group, R 11 is a fluoroalkyl group having 1 to 20 carbon atoms, The second monomer (b) is a compound represented by the following formula: CH2=C(-X 12 )-C(=O)-Y 12 -Z 12 -Rf 12 Where, X 12 is a hydrogen atom or a monovalent organic group, Y 12 is -O- or -NH-, Z 12 is a direct bond or a divalent organic group, R 12 is a fluoroalkyl group having 1 to 20 carbon atoms, The third monomer (c) is a compound represented by the following formula: CH2=C(-X 21 )-C(=O)-Y 21 -R 21 Where, X 21 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 21 is -O- or -NH-, R 21 is a chain hydrocarbon group having 12 to 40 carbon atoms, The fourth monomer (d) is a compound represented by the following formula: CH2=C(-X 22 )-C(=O)-Y 22 -R 22 Where, X 22 is a hydrogen atom, a monovalent organic group or a halogen atom, Y 22 is -O- or -NH-, R 22 It is a cyclic hydrocarbon group having 3 to 40 carbon atoms.

4. The fluorinated polymer according to any one of claims 1 to 3, characterized in that: The monovalent organic group is an alkyl group having 1 to 4 carbon atoms, The divalent organic group is a linear or branched alkylene group having 1 to 20 carbon atoms. The cyclic hydrocarbon group having 3 to 40 carbon atoms is a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or an aromatic aliphatic group having 7 to 25 carbon atoms.

5. The fluorinated polymer according to any one of claims 1 to 4, characterized in that: The third monomer (c) is: At least one long-chain acrylate monomer selected from the group consisting of lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, lauryl α-chloroacrylate, hexadecyl α-chloroacrylate, stearyl α-chloroacrylate, eicosyl α-chloroacrylate and behenyl α-chloroacrylate; or At least one long-chain acrylamide monomer selected from the group consisting of lauryl (meth)acrylamide, hexadecyl (meth)acrylamide, stearyl (meth)acrylamide, eicosyl (meth)acrylamide, and behenyl (meth)acrylamide, The fourth monomer (d) is: At least one compound selected from the group consisting of cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate and 2-ethyl-2-adamantyl (meth)acrylate.

6. The fluorinated polymer according to any one of claims 1 to 5, characterized in that: The amount of the first monomer (a) is 5 to 70 wt %, the amount of the second monomer (b) is 4 to 60 wt %, the amount of the third monomer (c) is 3 to 60 wt %, and the amount of the fourth monomer (d) is 3 to 60 wt % based on the fluorine-containing polymer.

7. The fluorinated polymer according to any one of claims 1 to 6, characterized in that: The fluorine-containing polymer has a repeating unit formed of a monomer (e) other than the monomers (a), (b), (c) and (d), The other monomer (e) is a halogenated olefin.

8. The fluorine-containing polymer according to claim 7, characterized in that: The amount of other monomers (e) is 0 to 50% by weight.

9. A fluorine-containing composition, characterized in that: It is a fluorine-containing composition comprising the following (1) and (2), (1) the fluorinated polymer according to any one of claims 1 to 8, (2) Liquid medium.

10. The fluorine-containing composition according to claim 9, characterized in that: The liquid medium (2) is an organic solvent, or water, an organic solvent, or a mixture of water and an organic solvent.

11. The fluorine-containing composition according to claim 9 or 10, characterized in that: The fluorine-containing composition is an aqueous dispersion in which a polymer is dispersed in water or a mixture of water and an organic solvent. The fluorine-containing composition contains (3) a surfactant.

12. The fluorine-containing composition according to any one of claims 9 to 11, characterized in that: The fluorine-containing composition is a water repellent, an oil repellent, an antifouling agent, a stain release agent, a stripping agent or a mold release agent.

13. A processed object, characterized in that: The fluorinated polymer according to any one of claims 1 to 8 is adhered thereto.

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