Water-repellent softener

Abstract

The present invention provides a softener composition comprising (1) a silicone polymer, (2) a water-repellent polymer, (3) an emulsifier, and (4) a liquid medium, the liquid medium being water or a mixture of water and an organic solvent. The water-repellent polymer is preferably produced by polymerizing a monomer constituting the water-repellent polymer in the presence of the silicone polymer. The water-repellent polymer is preferably at least one selected from the group consisting of a fluorine-containing polymer and a non-fluorine polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to a softening agent for imparting water repellency and softness to a substrate. BACKGROUND

[0002] In the past, in order to impart water and oil repellency and softness to a substrate such as a fiber, a composition in which a perfluoroalkyl group imparting water repellency, a long-chain alkyl group, and a modified silicone compound imparting softness are combined has been widely used (for example, Patent Literature 1 (Japanese Patent Application Laid-Open No. 58-42682), Patent Literature 2 (Japanese Patent Application Laid-Open No. 60-190408), and Patent Literature 3 (Japanese Patent Application Laid-Open No. 9-143877)). In addition, for the same purpose, a method using a copolymer of a fluorine-containing acrylate and an organosilicon monomer (for example, Patent Literature 4 (Japanese Patent Application Laid-Open No. 02-214791) and Patent Literature 5 (Japanese Patent Application Laid-Open No. 3-231986)), and the like have been proposed.

[0003] Patent Literature 6 (Japanese Patent Application Laid-Open No. 6-506239) discloses a composition containing a fluorine-containing compound having a fluorine compound oligomer portion, an organic portion, and a binding group.

[0004] Patent Literature 7 (Japanese Patent Application Laid-Open No. 2001-146548) discloses a composition containing an ester containing a perfluoroalkyl group and an oligomer or polyurethane.

[0005] Patent Literature 8 (Japanese Patent Application Laid-Open No. 2015-531011) discloses a composition containing an additive and an organopolysiloxane conditioning agent.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: Japanese Patent Application Laid-Open No. 58-42682

[0009] Patent Literature 2: Japanese Patent Application Laid-Open No. 60-190408

[0010] Patent Literature 3: Japanese Patent Application Laid-Open No. 9-143877

[0011] Patent Literature 4: Japanese Patent Application Laid-Open No. 02-214791

[0012] Patent Literature 5: Japanese Patent Application Laid-Open No. 3-231986

[0013] Patent Literature 6: Japanese Patent Application Laid-Open No. 6-506239

[0014] Patent Literature 7: Japanese Patent Application Laid-Open No. 2001-146548

[0015] Patent Literature 8: Japanese Patent Application Laid-Open No. 2015-531011 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] The existing softener, when used together with a water repellent agent to perform water repellent processing on a base material such as a fiber, causes a decrease in water repellency. In addition, the emulsion system of the softener emulsion and the water repellent agent emulsion are different, and thus, the stability of the emulsion is low by general mixing.

[0018] An object of the present application is to provide a softener composition capable of imparting good water repellency and softness at the time of water repellent processing.

[0019] TECHNICAL MEANS FOR SOLVING THE PROBLEMS

[0020] The present application relates to a softener composition comprising (1) a silicone polymer, (2) a water repellent polymer, (3) an emulsifier, and (4) a liquid medium, the liquid medium being water or a mixture of water and an organic solvent.

[0021] The water repellent polymer is preferably produced by polymerizing a monomer constituting the water repellent polymer in the presence of the silicone polymer. The water repellent polymer is preferably at least one selected from a fluorine-containing polymer and a non-fluorine polymer.

[0022] Preferred modes of the present application are described below.

[0023] Mode 1. A softener composition comprising:

[0024] (1) a silicone polymer;

[0025] (2) a water repellent polymer selected from at least one of a fluorine-containing polymer and a non-fluorine polymer, the water repellent polymer being obtained by polymerization in the presence of the silicone polymer;

[0026] (3) a liquid medium, which is water or a mixture of water and an organic solvent; and

[0027] (4) an emulsifier,

[0028] The amount of the silicone polymer is 20% by weight or more relative to the total of the silicone polymer and the water repellent polymer.

[0029] Mode 2. The softener composition according to Mode 1, wherein

[0030] The silicone polymer (1) is a polymer represented by the following formula:

[0031] (R 3 -)3Si-O-[-Si(-R 1 )2-O-] a -[-Si(-R 1(-X) 1 -R 2 )-O-] b -Si(-R 3 )3

[0032] [In the formula, R] 1 Each of the following is independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0033] R 2 Each is an independent functional group.

[0034] R 3 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a functional group.

[0035] X 1 Each is a hydrocarbon group with 1 to 10 carbon atoms, either in a valence bond or divalent.

[0036] a is an integer greater than or equal to 0, b is an integer greater than or equal to 0, and (a+b) ranges from 5 to 200.

[0037] The functional group is selected from at least one of the following: epoxy group, amino group, vinyl group, (meth)acrylamide group, (meth)acrylate group, and hydrocarbon group with 7 to 40 carbon atoms.

[0038] Method 3. The softener composition as described in Method 1 or 2, wherein,

[0039] Fluoropolymers have repeating units derived from fluorinated monomers as shown in the following formula:

[0040] CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf

[0041] [In the formula, X] 11 It consists of hydrogen atoms, straight-chain or branched alkyl groups having 1 to 21 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and CFX atoms. 1 X 2 Basis (where X) 1 and X 2 It consists of hydrogen, fluorine, chlorine, bromine, or iodine atoms; cyano groups; straight-chain or branched fluoroalkyl groups with 1 to 21 carbon atoms; substituted or unsubstituted benzyl groups; and substituted or unsubstituted phenyl groups.

[0042] Y 11 It can be -O- or -NH-;

[0043] Z 11 For valence bond,

[0044] Straight-chain or branched aliphatic groups with 1 to 20 carbon atoms

[0045] Aromatic groups or cyclic aliphatic groups with 6 to 30 carbon atoms

[0046] Formula - R 2 (R 1 N-SO2- or formula-R 2 (R 1 The group represented by N-CO- (where R is a radical) 1 R is an alkyl group having 1 to 10 carbon atoms. 2 It is a straight-chain alkylene or branched alkylene with 1 to 10 carbon atoms.

[0047] Formula - CH2CH(OR) 3 CH2-(Ar-O) p - The group shown (where R is a radical) 3 The 'Ar' indicates an acyl group with 1 to 10 hydrogen or carbon atoms, 'Ar' indicates an aryl group with substituents as needed, and 'p' indicates 0 or 1.

[0048] Formula: CH2-Ar-(O) q - The group shown (where Ar is an aryl group with substituents as needed, and q is 0 or 1), or

[0049] -(CH2) m -SO2-(CH2) n - group or -(CH2) m -S-(CH2) n - A base (where m is 1 to 10 and n is 0 to 10).

[0050] Rf is a straight-chain or branched fluoroalkyl group having 1 to 20 carbon atoms.

[0051] Non-fluoropolymers have repeating units derived from long-chain (meth)acrylic acid monomers represented by formula (a1):

[0052] CH2=C(-X 21 )-C(=O)-Y 21 -(R) 21 ) k (a1)

[0053] [In the formula, R] 21 It consists of hydrocarbon groups with 7 to 40 carbon atoms.

[0054] X 21 It can be a hydrogen atom, a methyl atom, or a halogen atom.

[0055] Y 21a group (in which the group is not a hydrocarbon group) composed of at least one or more selected from a hydrocarbon group having 1 carbon atom having a valence of 2 to 4 (particularly -CH2-, -CH=), -C6H4-, -0-, -C(=0)-, -S(=0)2-, or -NH-,

[0056] k is 1 to 3.

[0057] Mode 4. The softener composition according to Mode 3, wherein, in the fluorine-containing monomer, X 11 is a hydrogen atom, a methyl group, or a chlorine atom, and Rf has 1 to 6 carbon atoms.

[0058] Mode 5. The softener composition according to Mode 3, wherein,

[0059] in the long-chain (meth)acrylic monomer, Y 21 is -0-, -NH-, -0-C(=0)-, -C(=0)-NH-, -NH-C(=0)-, -0-C(=0)-NH-, -NH-C(=0)-0-, -NH-C(=0)-NH-, -0-C6H4-, -0-(CH2) m -0-, -NH-(CH2) m -NH-, -0-(CH2) m -NH-, -NH-(CH2) m -0-, -0-(CH2) m -0-C(=0)-, -0-(CH2) m -C(=0)-0-, -NH-(CH2) m -0-C(=0)-, -NH-(CH2) m -C(=0)-0-, -0-(CH2) m -0-C(=0)-NH-, -0-(CH2) m -NH-C(=0)-0-, -0-(CH2) m -C(=0)-NH-, -0-(CH2) m -NH-C(=0)-, -0-(CH2) m -NH-C(=0)-NH-, -0-(CH2) m -0-C6H4-, -0-(CH2) m -NH-S(=0)2-, -0-(CH2) m -S(=0)2-NH-, -NH-(CH2) m -0-C(=0)-NH-, -NH-(CH2) m -NH-C(=0)-0-, -NH-(CH2) m-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH-,

[0060] [In the formula, m is 1 to 5.].

[0061] Mode 6. The softener composition according to any one of Modes 1 to 5, wherein the amount of the silicone polymer (1) is 30 to 90% by weight, relative to the total weight of the silicone polymer (1) and the water repellent polymer (2),

[0062] the amount of the silicone polymer (1) is 30 to 90% by weight, relative to the total weight of the silicone polymer (1) and the water repellent polymer (2),

[0063] the amount of the liquid medium (3) is 5 to 99.9% by weight, relative to the softener composition,

[0064] the amount of the emulsifier (4) is 0.1 to 20 parts by weight, relative to 100 parts by weight of the silicone polymer (1) and the water repellent polymer (2).

[0065] Mode 7. The softener composition according to Mode 1 or 2, wherein the water repellent polymer (2) further has a repeating unit formed from a non-fluorinated non-crosslinkable monomer and / or a non-fluorinated crosslinkable monomer.

[0066] the water repellent polymer (2) further has a repeating unit formed from a non-fluorinated non-crosslinkable monomer and / or a non-fluorinated crosslinkable monomer.

[0067] Mode 8. The softener composition according to Mode 7, wherein the non-fluorinated non-crosslinkable monomer is a long-chain (meth)acrylic monomer represented by the formula:

[0068] the non-fluorinated non-crosslinkable monomer is a long-chain (meth)acrylic monomer represented by the formula: CH2=CA 21 -C(=O)-Y 21 -A 22

[0069] [In the formula, A 21 is a hydrogen atom or a methyl group,

[0070] A 22 is a linear or branched aliphatic hydrocarbon group having 7 to 40 carbon atoms,

[0071] Y 21 is -O- or -NH-.] ; or

[0072] ​The non-fluorine non-crosslinkable monomer is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group selected from the group consisting of a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group. 31 -C(=O)-Y 31 -A 32 The (meth)acrylic monomer containing a cyclic hydrocarbon group represented by the formula:

[0073] [In the formula, A 31 is a hydrogen atom or a methyl group,

[0074] A 32 is a cyclic hydrocarbon group having 4 to 20 carbon atoms,

[0075] Y 31 is -O- or -NH-.

[0076] Mode 9. The softener composition according to Mode 7, wherein

[0077] The non-fluorine crosslinkable monomer is a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group selected from the group consisting of a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group.

[0078] Mode 10. The softener composition according to any one of Modes 7 to 9, wherein

[0079] In the water repellent polymer (2),

[0080] The total amount of the fluorine-containing monomer and the non-fluorine monomer containing a long-chain hydrocarbon group is 32 to 98% by weight relative to the water repellent polymer,

[0081] The amount of the non-fluorine non-crosslinkable monomer is 2 to 68% by weight relative to the water repellent polymer,

[0082] The amount of the non-fluorine crosslinkable monomer is 0.1 to 20 parts by weight relative to 100 parts by weight of the total amount of the fluorine-containing monomer and the non-fluorine monomer containing a long-chain hydrocarbon group.

[0083] Mode 11. A method for producing a softener composition according to any one of Modes 1 to 10, wherein a water repellent polymer (2) is produced by polymerizing monomers constituting the water repellent polymer (2) in the presence of a silicone polymer (1) to obtain the softener composition.

[0084] Mode 12. A method for treating a substrate using the softener composition according to any one of Modes 1 to 10.

[0085] Mode 13. A substrate treated with the softener composition according to any one of Modes 1 to 10.

[0086] Effects of the Invention

[0087] According to the present application, the softener composition can impart good softness to fluorine-containing polymers and non-fluorine polymers without lowering water repellency.

[0088] The softener composition does not lower water repellency like the conventional softener emulsion using a large amount of emulsifier, and can impart good softness. Good softness, good water repellency and good oil repellency can be imparted effectively. The emulsion stability of the softener composition is high. DETAILED DESCRIPTION

[0089] The softener composition contains (1) a silicone polymer, (2) a water repellent polymer, (3) an emulsifier (surfactant) and (4) a liquid medium which is water or a mixture of water and an organic solvent. In the softener composition, the silicone polymer (1) and the water repellent polymer (2) function as effective components.

[0090] (1) Silicone polymer

[0091] The silicone polymer is a component which imparts softness mainly. In general, the silicone polymer is a linear polymer having a siloxane bond.

[0092] The silicone polymer preferably has no mercapto group. In general, the silicone polymer does not react with the monomer constituting the water repellent polymer.

[0093] The silicone polymer can also have no functional group, but preferably has at least one functional group. Examples of the functional group are an epoxy group, an amino group, a vinyl group, a (meth)acrylamide group, a (meth)acrylate group and a long-chain hydrocarbon group.

[0094] The silicone polymer is preferably a polymer represented by the following formula:

[0095] (R 3 -)3Si-O-[-Si(-R 1 )2-O-] a -[-Si(-R 1 )(-X 1 -R 2 )-O-] b -Si(-R 3 )3

[0096] [In the formula, R 1 each independently is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms,

[0097] R 2 each independently is a functional group,

[0098] R 3 each independently is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a functional group,

[0099] X 1 each is a valence bond or a divalent hydrocarbon group having 1 to 10 carbon atoms,

[0100] a is an integer of 0 or more, b is an integer of 0 or more, and (a+b) is 5 to 200.

[0101] In R 1 and R 3 , the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms can be unsubstituted, or can be substituted.

[0102] R 1 and R 3 specific examples of which can include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group; a phenyl group, a tolyl group, a naphthyl group, or a group in which part or all of the hydrogen atoms bound to these groups are substituted with a halogen atom, an amino group, a cyano group, or the like. R 1 and R 3 are preferably a methyl group or an ethyl group.

[0103] R 1 and R 3 may have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group (for example, a hydrocarbon group having an aromatic ring) having 8 to 40 carbon atoms, but preferably do not have these groups.

[0104] In R 1 and R 3 , the alkoxy group having 1 to 4 carbon atoms can be linear, or can be branched. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0105] From the viewpoint of being easily manufactured and easily available industrially, R 1 and R 3 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0106] R 2 is a functional group.

[0107] In R 2 and R 3 , the functional group is preferably an epoxy group, an amino group (for example, a monoamino group or a diamino group), a vinyl group, a (meth)acrylamide group, a (meth)acrylate group, and a long-chain hydrocarbon group.

[0108] The long-chain hydrocarbon group is preferably a saturated hydrocarbon group with 7 to 40 carbon atoms, for example 12 to 40, and especially 23 to 40. The long-chain hydrocarbon group can be straight-chain or branched, and is preferably alkyl. Specific examples of long-chain hydrocarbon groups are lauryl (12 carbon atoms), stearyl (18 carbon atoms), trialkyl (23 carbon atoms), lignoceryl (tetracosyl, 24 carbon atoms), cerotyl (hexacosyl, 26 carbon atoms), octacosyl (octacosyl, 28 carbon atoms), triacontyl (triacontyl, 30 carbon atoms), and tridodecyl (32 carbon atoms).

[0109] X 1 It is a hydrocarbon group with 1 to 10 carbon atoms, either valence bonded or divalent. The hydrocarbon group with 1 to 10 carbon atoms is preferably alkylene, and particularly preferably -(CH2). n - (n is an integer from 1 to 10, for example, an integer from 1 to 5.)

[0110] a is an integer greater than or equal to 0. From the perspective of ease of industrial manufacture and availability, a is preferably 40 or less, and more preferably 30 or less.

[0111] b is an integer greater than or equal to 0, preferably greater than or equal to 1. From the perspective of ease of manufacturing, availability, and operation in industry, b is preferably less than or equal to 40.

[0112] The sum of a and b is 5 to 200. From the perspective of ease of industrial manufacture, availability, and operation, the sum of a and b is preferably 10 to 100, more preferably 30 to 80, and particularly 40 to 60. a can be 0 to 150, for example 1 to 100. The lower limit of b can be 0, 1, 2, or 3, and the upper limit of b can be 150, 10, or 5.

[0113] There are multiple R 1 base, R 2 base, R 3 Base and X 1 The bases can be the same or different.

[0114] Preferred R 1 base and R 2 base and R 3 The total percentage of methyl groups is more than 50 mol%.

[0115] The order of repeating units enclosed in a or b is not limited to the order shown in the chemical formula and is arbitrary. That is, organosilicon polymers can be random polymers or block polymers.

[0116] Specific examples of the organosilicon polymer having no functional group are dimethylsilicone and methylphenylsilicone.

[0117] The organosilicon polymer preferably has a functional group. Specific examples of the organosilicon polymer having a functional group are as follows.

[0118]

[0119] b represents an integer of 1 to 150,

[0120] (a + b) is 5 to 200,

[0121] p is an integer of 0 to 5,

[0122] n is an integer of 3 to 36, particularly 19 to 36.

[0123] The organosilicon polymer can be synthesized by a publicly known method. For example, the organosilicon polymer having a long-chain hydrocarbon group can be obtained by subjecting an α-olefin (long-chain α-olefin) to hydrosilylation with an organosilicon having a SiH group.

[0124] As the organosilicon having a SiH group, for example, a methyl hydrogen-containing organosilicon polymer having a degree of polymerization of 10 to 200 or a copolymer of dimethylsiloxane and methyl hydrogen-containing siloxane, and the like can be exemplified. Among these, a methyl hydrogen-containing organosilicon is preferred in terms of being industrially easily manufactured and easily available.

[0125] The α-olefin is a compound that becomes a source of the long-chain hydrocarbon group in the organosilicon polymer. Specific examples of the α-olefin are 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triacontene, and 1-diacontene.

[0126] The hydrosilylation reaction can be performed by subjecting the α-olefin to reaction with the above organosilicon having a SiH group in stages or at once as needed in the presence of a catalyst.

[0127] The organosilicon having a SiH group and the α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent or the number average molecular weight of the organosilicon having a SiH group, and the like, respectively.

[0128] As the catalyst used in the hydrosilylation reaction, for example, a compound of platinum, palladium, or the like can be exemplified, of which a platinum compound is preferred. As the platinum compound, for example, platinum (IV) chloride or the like can be exemplified.

[0129] The reaction conditions of the hydrosilylation reaction are not particularly limited and can be appropriately adjusted. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. As for the reaction time, for example, when the reaction temperature is 50 to 150°C, it can be set to 3 to 12 hours.

[0130] The hydrosilylation reaction is preferably performed under an atmosphere of an inert gas. As the inert gas, for example, nitrogen, argon, and the like can be listed. Although the reaction can also be performed without a solvent, a solvent can be used. As the solvent, for example, dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate, and the like can be listed.

[0131] The weight average molecular weight (Mw) of the silicone polymer is generally 200 to 100,000, for example, 500 to 50,000, and particularly, 1,000 to 20,000. The weight average molecular weight (Mw) of the silicone polymer is generally measured by GPC (gel permeation chromatography) and is converted to styrene.

[0132] The silicone polymer is preferably provided to the production of the water repellent polymer in a form of a liquid or a solid (for example, an oil or a wax) that does not contain components other than the silicone polymer. Alternatively, the silicone polymer can be provided to the production of the water repellent polymer in a form of a solution or an aqueous emulsion.

[0133] (2) Water-repellent polymer

[0134] The water repellent polymer is a fluorine-containing polymer or a non-fluorine polymer. The fluorine-containing polymer is a polymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group. The non-fluorine polymer is a polymer having a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group.

[0135] The water repellent polymer is a homopolymer having a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a non-fluorine monomer having a hydrocarbon group having 7 to 40 carbon atoms (i.e., a non-fluorine monomer containing a long-chain hydrocarbon group); a copolymer having a repeating unit derived from two or more kinds of monomers selected from the group consisting of a fluorine-containing monomer having a fluoroalkyl group and a non-fluorine monomer containing a long-chain hydrocarbon group; or a copolymer having a repeating unit derived from another polymerizable compound copolymerizable with a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group or a non-fluorine monomer containing a long-chain hydrocarbon group.

[0136] The water repellent polymer can be a random polymer, or can be a block polymer.

[0137] The water repellent polymer (2) can be composed only of (2A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and / or (2B) a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group,

[0138] but preferably contains, in addition to the repeating unit (2A) and / or (2B),

[0139] Also, the water repellent polymer (2) has one or both of (2A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (2B) a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group. That is, the water repellent polymer (2) has one or both of (2A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (2B) a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group.

[0140] Also, the water repellent polymer (2) has one or both of (2A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (2B) a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group. That is, the water repellent polymer (2) has one or both of (2A) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group and (2B) a repeating unit derived from a non-fluorine monomer containing a long-chain hydrocarbon group.

[0141] (2A) Fluorine-containing monomer

[0142] The fluorine-containing monomer is generally a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group or an α-substituted acrylic acid group. The fluorine-containing monomer is generally a fluorine-containing acrylic monomer.

[0143] The fluorine-containing monomer is preferably a compound (acrylate or acrylamide) represented by the following formula:

[0144] CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf

[0145] [in the formula, X 11 is a hydrogen atom, a monovalent organic group or a halogen atom,

[0146] Y 11 is -O- or -NH-,

[0147] Z 11 is a bond or a divalent organic group,

[0148] Rf is a fluoroalkyl group having 1 to 20 carbon atoms.].

[0149] X 11 may be a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (wherein X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group.

[0150] X 11 Specific examples of X 11 are H, CH3, Cl, Br, I, F, CN, CF3. X 11 is preferably a hydrogen atom, a methyl group or a chlorine atom.

[0151] Y 11 The preferred option is -O-.

[0152] Z 11 It can be, for example, a straight-chain or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, such as the formula -(CH2). x - (where x is 1 to 10.) the group shown, or the formula -R 2 (R 1 N-SO2- or formula-R 2 (R 1 The group represented by N-CO- (where R is a radical) 1 R is an alkyl group having 1 to 10 carbon atoms. 2 It is a straight-chain alkylene group or a branched alkylene group having 1 to 10 carbon atoms, or with the formula -CH2CH(OR) 3 CH2-(Ar-O) p -(where R) 3 The group can be represented by a hydrogen atom or an acyl group (e.g., formyl or acetyl), where Ar represents an aryl group with substituents as needed, and p represents 0 or 1. It can also be represented by the formula -CH₂-Ar-(O). q —(where Ar is an aryl group with substituents as needed, and q is 0 or 1.) —(CH2) m -SO2-(CH2) n - group or -(CH2) m -S-(CH2) n -Base (where m is 1 to 10 and n is 0 to 10).

[0153] Z 11 Preferably, it is an aliphatic group with 1 to 10 carbon atoms, an aromatic group with 6 to 18 carbon atoms, or a cyclic aliphatic group, -CH2CH2N(R) 1 SO2-based (where R) 1 It is an alkyl group having 1 to 4 carbon atoms. (-CH2CH(OZ)) 1 CH2-(Ph-O) p -Base (where Z) 1 It can be a hydrogen atom or an acetyl group, Ph represents a phenylene group, and p is 0 or 1. ), -(CH2) n -Ph-O- group (where Ph is phenylene and n is 0–10), -(CH2) m -SO2-(CH2) n - group 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 (particularly having 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or the cyclic aliphatic group can be substituted or unsubstituted. The S group or the SO2group can be directly bonded to the Rfgroup.

[0154] The Rfgroup is preferably a perfluoroalkyl group. The number of carbon atoms of the Rfgroup is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, particularly preferably 6. Examples of the Rfgroup are -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.

[0155] As specific examples of the fluorine-containing monomer, the following, for example, can be exemplified, but are not limited thereto.

[0156] CH2=C(-H)-C(=O)-O-(CH2)2-Rf

[0157] CH2=C(-H)-C(=O)-O-C6H4-Rf

[0158] CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf

[0159] CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf

[0160] CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf

[0161] CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf

[0162] CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf

[0163] CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf

[0164] CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf

[0165] CH2=C(-H)-C(=0)-0-(CH2)2-S-Rf

[0166] CH2=C(-H)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0167] CH2=C(-H)-C(=0)-NH-(CH2)2-Rf

[0168] CH2=C(-CH3)-C(=0)-0-(CH2)2-S-Rf

[0169] CH2=C(-CH3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0170] CH2=C(-CH3)-C(=0)-0-(CH2)3-SO2-Rf

[0171] CH2=C(-CH3)-C(=0)-0-(CH2)2-SO2-(CH2)2-Rf

[0172] CH2=C(-CH3)-C(=0)-NH-(CH2)2-Rf

[0173] CH2=C(-F)-C(=0)-0-(CH2)2-S-Rf

[0174] CH2=C(-F)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0175] CH2=C(-F)-C(=0)-0-(CH2)2-SO2-Rf

[0176] CH2=C(-F)-C(=0)-0-(CH2)2-SO2-(CH2)2-Rf

[0177] CH2=C(-F)-C(=0)-NH-(CH2)2-Rf

[0178] CH2=C(-Cl)-C(=0)-0-(CH2)2-S-Rf

[0179] CH2=C(-Cl)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0180] CH2=C(-Cl)-C(=0)-0-(CH2)2-SO2-Rf

[0181] CH2=C(-Cl)-C(=0)-0-(CH2)2-SO2-(CH2)2-Rf

[0182] CH2=C(-CI)-C(=0)-0-(CH2)2-S-Rf

[0183] CH2=C(-CF3)-C(=0)-0-(CH2)2-S-Rf

[0184] CH2=C(-CF3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0185] CH2=C(-CF3)-C(=0)-0-(CH2)2-S02-Rf

[0186] CH2=C(-CF3)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf

[0187] CH2=C(-CF3)-C(=0)-NH-(CH2)2-Rf

[0188] CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-Rf

[0189] CH2=C(-CF2H)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0190] CH2=C(-CF2H)-C(=0)-0-(CH2)2-S02-Rf

[0191] CH2=C(-CF2H)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf

[0192] CH2=C(-CF2H)-C(=0)-NH-(CH2)2-Rf

[0193] CH2=C(-CN)-C(=0)-0-(CH2)2-S-Rf

[0194] CH2=C(-CN)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0195] CH2=C(-CN)-C(=0)-0-(CH2)2-S02-Rf

[0196] CH2=C(-CN)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf

[0197] CH2=C(-CN)-C(=0)-NH-(CH2)2-Rf

[0198] CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S-Rf

[0199] CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S-(CH2)2-Rf

[0200] CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S02-Rf

[0201] CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf

[0202] CH2=C(-CF2CF3)-C(=0)-NH-(CH2)2-Rf

[0203] CH2=C(-F)-C(=0)-0-(CH2)3-S-Rf

[0204] CH2=C(-F)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0205] CH2=C(-F)-C(=0)-0-(CH2)3-S02-Rf

[0206] CH2=C(-F)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf

[0207] CH2=C(-F)-C(=0)-NH-(CH2)3-Rf

[0208] CH2=C(-Cl)-C(=0)-0-(CH2)3-S-Rf

[0209] CH2=C(-Cl)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0210] CH2=C(-Cl)-C(=0)-0-(CH2)3-S02-Rf

[0211] CH2=C(-Cl)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf

[0212] CH2=C(-CF3)-C(=0)-0-(CH2)3-S-Rf

[0213] CH2=C(-CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0214] CH2=C(-CF3)-C(=0)-0-(CH2)3-S-Rf

[0215] CH2=C(-CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0216] CH2=C(-CF2H)-C(=0)-0-(CH2)3-S-Rf

[0217] CH2=C(-CF2H)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0218] CH2=C(-CF2H)-C(=0)-0-(CH2)3-S02-Rf

[0219] CH2=C(-CF2H)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf

[0220] CH2=C(-CN)-C(=0)-0-(CH2)3-S-Rf

[0221] CH2=C(-CN)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0222] CH2=C(-CN)-C(=0)-0-(CH2)3-S02-Rf

[0223] CH2=C(-CN)-C(=0)-0-(CH2)3-S02-(CH2)2-Rf

[0224] CH2=C(-CF2CF3)-C(=0)-0-(CH2)3-S-Rf

[0225] CH2=C(-CF2CF3)-C(=0)-0-(CH2)3-S-(CH2)2-Rf

[0226] CH2=C(-CF2CF3)-C(=0)-0-(CH2)3-S02-Rf

[0227] CH2=C(-CF2CF3)-C(=0)-0-(CH2)2-S02-(CH2)2-Rf

[0228] [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0229] (2B) Non-fluorine monomer containing long-chain hydrocarbon group

[0230] The non-fluorine monomer containing a long-chain hydrocarbon group does not have a fluoroalkyl group. The non-fluorine monomer containing a long-chain hydrocarbon group does not contain a fluorine atom.

[0231] The number of carbon atoms of the long-chain hydrocarbon group is preferably 7 to 40, for example, 10 to 40, particularly 12 to 30, and particularly preferably 15 to 30 (or 15 to 35). The long-chain hydrocarbon group is preferably a linear or branched hydrocarbon group. The long-chain hydrocarbon group is a saturated or unsaturated group. The long-chain hydrocarbon group is preferably a saturated hydrocarbon group, particularly an alkyl group.

[0232] The non-fluorine monomer containing a long-chain hydrocarbon group is generally a non-fluorine acrylic monomer having a long-chain hydrocarbon group.

[0233] The non-fluorine monomer containing a long-chain hydrocarbon group (2B) is preferably a monomer represented by formula (al), particularly a (meth)acrylic monomer.

[0234] CH2=C(-X 21 )-C(=O)-Y 21 -(R 21 ) k (al)

[0235] [In the formula, R 21 is a hydrocarbon group having 7 to 40 carbon atoms,

[0236] X 21 is a hydrogen atom, a methyl group, or a halogen atom,

[0237] Y 21 is a group composed of at least one or more selected from a hydrocarbon group having 1 carbon atom (particularly -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (but not a hydrocarbon group),

[0238] k is 1 to 3.

[0239] Y 21 is a divalent to tetravalent group. Y 21 is preferably a divalent or trivalent group, particularly a divalent group.

[0240] Y 21 may be a group composed of at least one or more selected from a hydrocarbon group having 1 carbon atom, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (wherein it is not a hydrocarbon group). As examples of the hydrocarbon group having 1 carbon atom, -CH2-, -CH= having a branched structure, or -C≡ having a branched structure can be listed.

[0241] Y 21may be -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'-.

[0242] [In the formula, Y' is a bond, -O-, -NH-, or -S(=O)2-,

[0243] R' is -(CH2) m -(m is an integer of 1 to 5) or -C6H4- (phenylene group).]

[0244] Y 21 Specific examples are -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- [in the formula, m is 1 to 5, particularly 2 or 4].

[0245] Y 21 k is 1 when Y 21 k is 2 when Y 21 k is 3 when Y

[0246] Examples of the acrylic monomer having a long-chain hydrocarbon group are as follows:

[0247] The acrylic monomer represented by the formula (a2):

[0248] CH2=C(-X 24 )-C(=O)-Y 22 -R 22 (a2)

[0249] [in the formula, R 22 is a hydrocarbon group having 7 to 40 carbon atoms,

[0250] X 24 is a hydrogen atom, a methyl group or a halogen atom,

[0251] Y 22 is -O- or -NH-; and

[0252] The polyurethane monomer represented by the formula (a3):

[0253] CH2=C(-X 25 )-C(=O)-Y 23 -Z(-Y 24 -R 23 ) m (a3)

[0254] [in the formula, R 23 is a hydrocarbon group having 7 to 40 carbon atoms,

[0255] X 25 is a hydrogen atom, a methyl group or a halogen atom,

[0256] Y 23 is -O- or -NH-,

[0257] Y 24 -0-C(=0)-NH-, -NH-C(=0)-0-, or -NH-C(=0)-NH-,

[0258] Z is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0259] m is 1 or 2.

[0260] In the present specification, the urethane monomer also includes a urea monomer having a urea group.

[0261] The urethane monomer (a3) can be produced by reacting a hydroxyalkyl (meth) acrylate or a hydroxyalkyl (meth) acrylamide with a long-chain alkyl isocyanate. Examples of the alkyl group in the hydroxyalkyl (meth) acrylate and the hydroxyalkyl (meth) acrylamide include an alkyl group having 2 to 10 carbon atoms, such as ethyl, propyl, butyl, hexyl, and decyl. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.

[0262] Alternatively, the urethane monomer (a3) can be produced by reacting a (meth) acrylate having an isocyanate group in the side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkyl amine or a long-chain alkyl alcohol. Examples of the long-chain alkyl amine include lauryl amine, myristyl amine, cetyl amine, stearyl amine, oleyl amine, and behenyl amine. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0263] The acrylic monomer containing a long-chain alkyl group is preferably, for example, the following.

[0264] stearyl (meth) acrylate, behenyl (meth) acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate;

[0265] stearyl (meth) acrylamide, behenyl (meth) acrylamide;

[0266]

[0267]

[0268] [in the above formula, m is a number from 1 to 5, and n is a number from 7 to 40.]

[0269] The compound of the above formula is an acrylic compound having a hydrogen atom at the α position, but specific examples can be a methacrylic compound having a methyl group at the α position and an α-chloroacrylic compound having a chlorine atom at the α position.

[0270] The non-fluorine monomer (2B) containing a long-chain hydrocarbon group preferably has a melting point of 10°C or higher, and more preferably 25°C or higher.

[0271] As the non-fluorine monomer (2B) containing a long-chain hydrocarbon group, X 21 , X 24 and X 25 is a propenoate ester having a hydrogen atom, and is particularly preferably a stearyl acrylate.

[0272] The water-repellent polymer (2) preferably has one or both of (2C) a repeating unit derived from a non-fluorine non-crosslinking monomer and (2D) a repeating unit derived from a non-fluorine crosslinking monomer in addition to the repeating units (2A) and / or (2B) (i.e., the repeating units derived from the monomers (2A) and / or (2B)).

[0273] (2C) Non-fluorine non-crosslinking monomer

[0274] The non-fluorine non-crosslinking monomer (2C) is a monomer other than the non-fluorine monomer (2B) containing a long-chain hydrocarbon group. The non-fluorine non-crosslinking monomer (2C) is a monomer not containing a fluorine atom. The non-fluorine non-crosslinking monomer (2C) does not have a crosslinking functional group. The non-fluorine non-crosslinking monomer (2C) is non-crosslinking unlike the crosslinking monomer (2D). The non-fluorine non-crosslinking monomer (2C) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinking monomer (2C) is preferably a non-fluorine vinyl monomer. The non-fluorine non-crosslinking monomer (2C) is generally a compound having one carbon-carbon double bond.

[0275] The preferred non-fluorine non-crosslinking monomer (2C) is a compound represented by the following formula:

[0276] CH2=CA-T

[0277] [in the formula, A is a hydrogen atom, a methyl group, or a halogen atom (e.g., a chlorine atom, a bromine atom, and an iodine atom) other than a fluorine atom,

[0278] T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms having an ester bond.].

[0279] Examples of the chain or cyclic hydrocarbon group having 1 to 40 carbon atoms are a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms, a cyclic aliphatic group having 4 to 40 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms.

[0280] Examples of the chain or cyclic organic group having 1 to 41 carbon atoms having an ester bond are -C(=O)-O-Q and -O-C(=O)-Q (where Q is a linear or branched aliphatic hydrocarbon group having 1 to 40 carbon atoms, a cyclic aliphatic group having 4 to 40 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, or an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms).

[0281] Preferred examples of the non-fluorine non-crosslinkable monomer (2C) include, for example, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether. The non-fluorine non-crosslinkable monomer (2C) is not limited to these examples.

[0282] The non-fluorine non-crosslinkable monomer (2C) can be a (meth) acrylate having an alkyl group. The number of carbon atoms of the alkyl group can be 1 to 17, for example, 1 to 10. For example, the non-fluorine non-crosslinkable monomer (2C) can be an acrylate represented by the following general formula:

[0283] CH2=CA 1 COOA 2

[0284] [in the formula, A 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),

[0285] A 2 is an alkyl group represented by CH2=CA n H 2n+1 (n = 1 to 17).

[0286] The fluorine-containing monomer can not have a repeating unit derived from a (meth) acrylate having an alkyl group having a number of carbon atoms of 1 to 17.

[0287] The non-fluorine non-crosslinkable monomer (2C) can be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a cyclic hydrocarbon group (preferably monovalent) and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. As the cyclic hydrocarbon group, a saturated or unsaturated, monocyclic group, polycyclic group, bridged cyclic group, or the like can be listed. The cyclic hydrocarbon group is preferably a saturated cyclic hydrocarbon group. The number of carbon atoms of the cyclic hydrocarbon group is preferably 4 to 20. As the cyclic hydrocarbon group, a cyclic aliphatic group having a number of carbon atoms of 4 to 20, in particular 5 to 12, an aromatic group having a number of carbon atoms of 6 to 20, an aromatic aliphatic group having a number of carbon atoms of 7 to 20 can be listed. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 10 or less. It is preferable that a carbon atom on the ring of the cyclic hydrocarbon group be directly bonded to the ester group in the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

[0288] Specific examples of the cyclic hydrocarbon group are cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentyl group, dicyclopentenyl group, adamantyl group. The acrylate group is preferably acrylate group or methacrylate group, and particularly preferably methacrylate group. As specific examples of the monomer having a cyclic hydrocarbon group, (methyl)acrylic acid cyclohexyl ester, (methyl)acrylic acid t-butylcyclohexyl ester, (methyl)acrylic acid benzyl ester, (methyl)acrylic acid isobornyl ester, (methyl)acrylic acid dicyclopentyl ester, (methyl)acrylic acid dicyclopentenyl ester, (methyl)acrylic acid dicyclopentyloxyethyl ester, (methyl)acrylic acid tricyclopentyl ester, (methyl)acrylic acid adamantyl ester, 2-methyl-2-adamantyl (methyl)acrylate, 2-ethyl-2-adamantyl (methyl)acrylate, and the like can be exemplified.

[0289] The non-fluorine non-crosslinkable monomer (2C) can be a halogenated olefin. The halogenated olefin can be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, and particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin are halogenated vinyl groups, such as chlorinated vinyl group, brominated vinyl group, iodinated vinyl group, partially halogenated ethylene, such as partially chlorinated ethylene, partially brominated ethylene, partially iodinated ethylene.

[0290] (2D) Non-fluorine crosslinking monomer

[0291] The water repellent polymer can have a repeating unit derived from a non-fluorine crosslinkable monomer (2D). The non-fluorine crosslinkable monomer (2D) is a monomer not containing a fluorine atom. The non-fluorine crosslinkable monomer (2D) can be a compound having at least 2 reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (2D) can be a compound having at least 2 carbon-carbon double bonds, or a compound having at least 1 carbon-carbon double bond and at least 1 reactive group. Examples of the reactive group are hydroxyl group, epoxy group, chloromethyl group, blocked isocyanate group, amino group, carboxyl group, and the like.

[0292] As the non-fluorine crosslinkable monomer (2D), for example, the following can be exemplified: diacetone acrylamide, (methyl)acrylamide, N-hydroxymethyl acrylamide, (methyl)acrylic acid hydroxymethyl ester, (methyl)acrylic acid hydroxyethyl ester, 3-chloro-2-hydroxypropyl (methyl)acrylate, 2-acetoacetoxyethyl (methyl)acrylate, N,N-dimethylaminoethyl (methyl)acrylate, N,N-diethylaminoethyl (methyl)acrylate, 2-chloroethyl (methyl)acrylate, butadiene, isoprene, chlorobutadiene, glycidyl (methyl)acrylate, and the like, but not limited to these.

[0293] By copolymerizing the non-fluorine non-crosslinkable monomer (2C) and / or the non-fluorine crosslinkable monomer (2D), it is possible to improve water and oil repellency, stain resistance, and various properties such as the resistance to cleaning, the resistance to washing, the solubility in solvents, the hardness, the touch, and the like as needed.

[0294] The monomers (2A), (2B), (2C), and (2D) are prepared, and polymerization is performed in the presence of the silicone polymer (1) to obtain the water repellent polymer (2).

[0295] Although not bound by theory, it can be considered that the water repellent polymer (2) forms the same particle as the silicone polymer (1) in the emulsion.

[0296] The amount of the silicone polymer (1) can be 20 to 95% by mass, for example, 30 to 90% by mass, particularly 40 to 88% by mass, relative to the total weight of the silicone polymer (1) and the water repellent polymer (2). The amount of the silicone polymer (1) can be 51% by mass or more, for example, 55% by mass or more.

[0297] The amount of the water repellent polymer (2) can be 5 to 80% by mass, for example, 10 to 70% by mass, particularly 12 to 60% by mass, relative to the total weight of the silicone polymer (1) and the water repellent polymer (2).

[0298] Each of the monomers (2A), (2B), (2C), and (2D) can be only one or two or more in combination.

[0299] The amount of each of the fluorine-containing monomer (2A) and the non-fluorine monomer containing a long-chain hydrocarbon group (2B) (or the total of the monomer (2A) and the monomer (2B)) in the water repellent polymer, in which the total of the monomer (2A) and the monomer (2B) is 100% by mass or less, can be 30 to 100% by mass, preferably 32 to 98% by mass, for example, 35 to 95% by mass, particularly 40 to 90% by mass.

[0300] In the water repellent polymer, only one of the fluorine-containing monomer (2A) or the non-fluorine monomer containing a long-chain hydrocarbon group (2B) can be present, or both the fluorine-containing monomer (2A) and the non-fluorine monomer containing a long-chain hydrocarbon group (2B) can be present in the water repellent polymer. When both the fluorine-containing monomer (2A) and the non-fluorine monomer containing a long-chain hydrocarbon group (2B) are present in the water repellent polymer, the amount of the fluorine-containing monomer (2A) relative to the total of the monomer (2A) and the monomer (2B) can be 10 to 90% by mass, for example, 30 to 70% or 25 to 49%.

[0301] In the water repellent polymer, the amount of the fluorine-containing monomer (2A) and the non-fluorine monomer containing a long-chain hydrocarbon group (2B) can be 10 to 90% by mass, for example, 30 to 70% or 25 to 49%, relative to 100 parts by mass of the total of the fluorine-containing monomer (2A) and the non-fluorine monomer containing a long-chain hydrocarbon group (2B).

[0302] The amount of the non-fluorinated non-crosslinkable monomer (2C) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,

[0303] The amount of the non-fluorinated crosslinkable monomer (2D) can be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.

[0304] The amount of the non-fluorinated non-crosslinkable monomer (2C) can be 2 to 68% by weight, for example, 5 to 65% by weight, particularly 10 to 60% by weight, relative to the water repellent polymer (or the total of the monomer (2A) and the monomer (2B) and the monomer (2C)).

[0305] The weight average molecular weight (Mw) of the water repellent polymer is generally 1000 to 1,000,000, for example, 2,000 to 500,000, particularly 3,000 to 200,000. The weight average molecular weight (Mw) of the water repellent polymer is generally determined by GPC (gel permeation chromatography) and is converted to styrene.

[0306] (3) Liquid medium

[0307] The softener composition contains a liquid medium. The liquid medium can be an organic solvent, but is preferably water or a mixture of water and an organic solvent.

[0308] The softener composition is generally a solution or a dispersion. The solution is a solution in which the polymer is dissolved in an organic solvent. The dispersion is an aqueous dispersion in which the polymer is dispersed in an aqueous medium (water, or a mixture of water and an organic solvent).

[0309] Examples of the organic solvent are: esters (for example, esters having 2 to 40 carbon atoms, specifically, ethyl acetate, butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (for example, toluene and xylene), petroleum solvents (for example, alkanes having 5 to 10 carbon atoms, specifically, naphtha, kerosene).

[0310] The liquid medium can be water alone, or a mixture of water and an organic solvent (water-miscible). The amount of the organic solvent can 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.

[0311] The amount of the liquid medium is, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, relative to the softener composition.

[0312] (4) Emulsifier (surfactant)

[0313] Generally, the softener composition is an aqueous dispersion. The softener composition contains an emulsifier (surfactant).

[0314] Before the softener composition is manufactured, when the silicone polymer is in the form of an aqueous dispersion, the aqueous dispersion preferably contains a surfactant.

[0315] In the softener composition, the surfactant includes a nonionic surfactant. The surfactant can also include one or more surfactants selected from the group consisting of cationic surfactants, anionic surfactants, and amphoteric surfactants. The surfactant can be only a nonionic surfactant, or can be a combination of a nonionic surfactant and a cationic surfactant.

[0316] (4A) Non-ionic surfactant

[0317] As examples of nonionic surfactants, ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides can be listed.

[0318] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0319] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols (e.g., fatty alcohols) having a carbon atom number of 1 to 50 (particularly a carbon atom number of 10 to 30) of valence 1 to 6 (particularly valence 2 to 5). Examples of fatty acids are saturated or unsaturated fatty acids having a carbon atom number of 2 to 50, particularly a carbon atom number of 5 to 30.

[0320] Examples of ester ethers are compounds obtained by adding an oxyalkylene group (particularly an oxyethylene group) to esters of alcohols and fatty acids. Examples of alcohols are alcohols (e.g., fatty alcohols) having a carbon atom number of 1 to 50 (particularly a carbon atom number of 3 to 30) of valence 1 to 6 (particularly valence 2 to 5). Examples of fatty acids are saturated or unsaturated fatty acids having a carbon atom number of 2 to 50, particularly a carbon atom number of 5 to 30.

[0321] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide can be a monoalkanolamide or a dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids having a carbon atom number of 2 to 50, particularly a carbon atom number of 5 to 30. The alkanolamine can be an alkanol having a carbon atom number of 2 to 50, particularly 5 to 30, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0322] The polyol can be an alcohol of 2 to 5 valence and a carbon atom number of 10 to 30.

[0323] The amine oxide can be an oxide (e.g., a carbon atom number of 5 to 50) of an amine (a secondary amine or preferably a tertiary amine).

[0324] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably from 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably from 2 to 100.

[0325] The nonionic surfactant is preferably a nonionic surfactant selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides and having an oxyalkylene group.

[0326] The nonionic surfactant can be an oxyalkylene adduct of a straight-chain and / or branched-chain aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a straight-chain and / or branched-chain aliphatic 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, the structure of the oxyalkylene addition moiety and the polyalkylene glycol moiety is preferably polyoxyethylene (POE) or polyoxypropylene (POP) or a POE / POP copolymer (either a random copolymer or a block copolymer).

[0327] In addition, from the viewpoint of environmental problems (biodegradability, environmental hormones, etc.), the nonionic surfactant is preferably free of an aromatic group structure.

[0328] The nonionic surfactant can be a compound represented by the following formula:

[0329] R 1 O - (CH2CH2O) p - (R 2 O) q - R 3

[0330] [In the formula, R 1 is an alkyl group having from 1 to 22 carbon atoms or an alkenyl group having from 2 to 22 carbon atoms or an acyl group,

[0331] R 2 each independently is the same or different and is an alkylene group having from 3 or more (for example, from 3 to 10) carbon atoms,

[0332] R 3 is a hydrogen atom, an alkyl group having from 1 to 22 carbon atoms or an alkenyl group having from 2 to 22 carbon atoms, and p is a number of 2 or more,

[0333] q is 0 or a number of 1 or more.]

[0334] R 1 Preferably, the number of carbon atoms is from 8 to 20, and in particular from 10 to 18. As a preferred specific example of R 1 , lauryl, tridecyl, oleyl can be given.

[0335] R 2 Examples of R include propylene, butylene.

[0336] In the nonionic surfactant, p can be a number of 3 or more (e.g., 5 to 200). q can be a number of 2 or more (e.g., 5 to 200). That is, -(R 2 O) q - can form a polyoxyalkylene chain.

[0337] The nonionic surfactant can be a polyoxyethylene alkylene alkyl ether having a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. As the hydrophobic oxyalkylene chain, an oxypropylene chain, an oxybutylene chain, a styrene chain, and the like can be listed, of which an oxypropylene chain is preferred.

[0338] Specific examples of the nonionic surfactant include condensation products of ethylene oxide with hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 )thiol, sorbitan monofatty acid (C7-C 19 )or alkyl (C 12 -C 18 )amine, and the like.

[0339] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, with respect to the molecular weight of the nonionic surfactant (copolymer).

[0340] The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example, 500 to 3,000.

[0341] The nonionic surfactant can be one alone, or can be a mixture of two or more.

[0342] (4B) Cationic surfactant

[0343] The cationic surfactant is preferably a compound having no amide group.

[0344] The cationic surfactant can be an amine salt, a quaternary ammonium salt, an ethylene oxide addition type ammonium salt. As specific examples of the cationic surfactant, there are no particular limitations, and amine salt type surfactants of alkyl amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like, quaternary ammonium salt type surfactants of alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, benzethonium chloride, and the like, and the like can be listed.

[0345] Preferred examples of the cationic surfactant are the following compounds:

[0346] R 21 -N + (-R 22 )(-R 23 )(-R 24 )X -

[0347] [In the formula, R 21 , R 22 , R 23 , and R 24 are hydrocarbon groups having 1 to 40 carbon atoms,

[0348] X is an anionic group.].

[0349] R 21 , R 22 , R 23 , and -R 24 are alkyl groups (e.g., methyl, butyl, stearyl, palmitoyl). Specific examples of X are halogen (e.g., chlorine atom), acid (e.g., hydrochloric acid, acetic acid).

[0350] The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group having 4 to 40 carbon atoms).

[0351] The cationic surfactant is preferably an ammonium salt. The cationic surfactant can be an ammonium salt represented by the following formula:

[0352] R 1 p -N + R 2 q X －

[0353] [In the formula, R 1 is a linear and / or branched aliphatic (saturated and / or unsaturated) group having 12 or more (e.g., C 12 to C 50 ) carbon atoms,

[0354] R 2 is H or an alkyl group having 1 to 4 carbon atoms, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50)

[0355] (particularly preferably CH3, C2H5),

[0356] X is a halogen atom (e.g., chlorine atom), a C1to C4fatty acid radical,

[0357] p is 1 or 2, q is 2 or 3, and p + q = 4.]. R 1The number of carbon atoms of the alkyl group can be 12 to 50, for example, 12 to 30.

[0358] Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyl dimethylammonium chloride, methyldodecyl di(hydropolyoxyethylene)ammonium chloride, benzyldodecyl di(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0359] As the amphoteric surfactant, alanine-based, imidazolinium betaine-based, amide betaine-based, betaine acetate, and the like can be exemplified, and specifically, lauryl betaine, stearyl betaine, lauryl carboxymethylhydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, fatty amide propyldimethylaminoacetic acid betaine, and the like can be exemplified.

[0360] The amount of the emulsifier (4) can be 0.1 to 20 parts by weight, for example, 1 to 10 parts by weight, with respect to 100 parts by weight of the total of the silicone polymer (1) and the water-repellent polymer (3).

[0361] The nonionic surfactant, the cationic surfactant, and the amphoteric surfactant can each be one or a combination of two or more.

[0362] The amount of the cationic surfactant can be 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more, with respect to the total amount of the surfactants. The weight ratio of the nonionic surfactant to the cationic surfactant is preferably 95:5 to 20:80, and more preferably 85:15 to 40:60.

[0363] The amount of the cationic surfactant can be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, with respect to 100 parts by weight of the polymer. The total amount of the surfactants can be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, with respect to 100 parts by weight of the polymer.

[0364] (5) Other components

[0365] In the surface treatment agent, an additive can be further contained as another component other than the silicone polymer, the water-repellent polymer, the liquid medium, and the surfactant.

[0366] Examples of the additive are a silicon-containing compound, a wax, an acrylic emulsion, and the like. Other examples of the additive are a drying speed adjusting agent, a crosslinking agent, a film forming aid, a compatibilizer, a surfactant, a freezing preventing agent, a viscosity adjusting agent, an ultraviolet absorber, an antioxidant, a pH adjusting agent, an antifoaming agent, a texture adjusting agent, a slip property adjusting agent, an antistatic agent, a hydrophilic agent, an antibacterial agent, a preservative, an insect repellent, a fragrance, a flame retardant, and the like.

[0367] Generally, a silicone polymer (silicone oil or silicone wax) which is preferably oily or waxy is added with a monomer constituting a water-repellent polymer, a surfactant, and water, an organic solvent as necessary, and the monomer is polymerized, whereby a softener composition can be produced.

[0368] The softener composition is preferably produced by emulsion polymerization. Alternatively, solution polymerization or suspension polymerization can also be used.

[0369] The emulsion polymerization employs a method in which the monomer is emulsified in water in the presence of a polymerization initiator and a surfactant (emulsifier) and polymerization is performed by stirring at 50 to 80°C for 1 to 10 hours after nitrogen substitution. The polymerization initiator can use water-soluble substances such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobis isobutyl amide dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, oil-soluble substances such as azobis isobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumyl hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator can be used in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

[0370] In order to obtain a polymer aqueous dispersion excellent in storage stability, it is desirable to use an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer which can impart a strong breaking energy, to micronize the monomer in water, and thereby perform polymerization. In addition, as the emulsifier, various emulsifiers of anionic, cationic, or nonionic can be used, and can be used in a range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. It is preferable to use an emulsifier of anionic and / or nonionic and / or cationic. In the case where the monomers are not completely compatible, it is preferable to add a compatibilizer such as a water-soluble organic solvent, a low-molecular-weight monomer, to these monomers, which can make them sufficiently compatible. By adding the compatibilizer, emulsifiability and copolymerizability can be improved.

[0371] As the water-soluble organic solvent, acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, and the like can be exemplified, and can be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, with respect to 100 parts by weight of water. In addition, as the low-molecular-weight monomer, methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like can be exemplified, and can be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, with respect to 100 parts by weight of the total amount of monomers.

[0372] In the polymerization, a chain transfer agent can be used. Depending on the amount of the chain transfer agent used, the molecular weight of the polymer can be varied. Examples of the chain transfer agent are a thiol group-containing compound such as lauryl mercaptan, thio glycol, thio glycerol (particularly, an alkyl mercaptan (e.g., having 1 to 40 carbon atoms)), an inorganic salt such as sodium hypophosphite, sodium bisulfite, and the like. The amount of the chain transfer agent used can be in a range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, with respect to 100 parts by weight of the total amount of monomers.

[0373] The softener composition (treatment agent) can be in the form of a solution, an emulsion, or an aerosol. The softener composition is preferably an aqueous dispersion. The softener composition contains a silicone polymer and a water-repellent polymer (active ingredients of the softener composition) and a medium (particularly, a liquid medium such as an organic solvent and / or water). The amount of the medium can be, for example, 5 to 99.9% by weight, particularly, 10 to 80% by weight, with respect to the treatment agent.

[0374] In the treatment agent, the concentration of the total amount of the silicone polymer and the water-repellent polymer can be 0.01 to 95% by weight, 0.1 to 60% by weight, for example, 5 to 50% by weight.

[0375] The softener composition can be applied to the treated object by a conventionally known method. Generally, after the treatment agent is diluted by being dispersed in an organic solvent or water, it is attached to the surface of the treated object using a known method such as dip coating, spray coating, foam coating, and the like, and is dried. In addition, if necessary, a suitable crosslinking agent (e.g., a blocked isocyanate) can be used together, and curing can be performed. Furthermore, an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, a wrinkle prevention agent, and the like can be added to the treatment agent of the present application and used together. The total concentration of the silicone polymer and the water-repellent polymer in the treatment liquid in contact with the substrate can be 0.01 to 10% by weight (particularly, when dip coating), for example, 0.05 to 10% by weight.

[0376] As the treated object to be treated with the softener composition (treatment agent), there can be mentioned fiber products, stone, filters (e.g., electrostatic filters), dust covers, components of fuel cells (e.g., gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, pottery, plastics, paint and plaster, and the like. As the fiber products, various examples can be mentioned. For example, there can be mentioned animal and plant natural fibers such as wool, hemp, wool, silk and the like, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene and the like, semi-synthetic fibers such as acetate and the like, inorganic fibers such as glass fibers, carbon fibers, asbestos fibers and the like, or mixed fibers of these.

[0377] The fiber product can be in any form of fiber, cloth and the like.

[0378] The softener composition (or silicone polymer and water repellent polymer) can be applied to the fibrous substrate (e.g., fiber product and the like) by any known method of treating a fiber product with a liquid. When the fiber product is cloth, the cloth can be immersed in the treatment agent, or the treatment agent can be attached or sprayed onto the cloth. The treated fiber product is dried, preferably heated at, for example, 100 to 200°C, in order to exhibit oil repellency.

[0379] Alternatively, the softener composition can be applied to the fiber product by a cleaning method, for example, can be applied to the fiber product by washing or in a dry cleaning method and the like.

[0380] The treated fiber product is typically cloth, which includes woven fabric, knitted fabric and non-woven fabric, cloth in the form of clothing and carpet, and can also be fiber or yarn or intermediate fiber product (e.g., sliver or roving and the like). The fiber product material can be natural fiber (e.g., wool or wool and the like), chemical fiber (e.g., viscose rayon or Lyocell and the like), or synthetic fiber (e.g., polyester, polyamide or acrylic fiber and the like), or can be a mixture of fibers (e.g., a mixture of natural fiber and synthetic fiber and the like). The softener composition is particularly effective for rendering cellulose-based fiber (e.g., wool or rayon and the like) oleophobic and oil repellent. In addition, the method of the present application generally renders the fiber product hydrophobic and water repellent.

[0381] Alternatively, the fibrous substrate can be leather. In order to render the leather hydrophobic and oleophobic, the softener composition can be applied to the leather from an aqueous solution or aqueous emulsion during each stage of leather processing, for example, during wet processing of the leather or during finishing of the leather.

[0382] Alternatively, the fibrous substrate can be paper. The softener composition can be applied to preformed paper, or can also be applied during each stage of paper making, for example, during drying of the paper.

[0383] The softener composition can impart oil repellency to the treated object. When the softener composition is used together with the water repellent fluorine-containing polymer, the oil repellency is remarkably improved.

[0384] "Treating" means applying the treating agent to the treated object by dipping, spraying, coating, or the like. By the treatment, the polymer as the effective ingredient of the treating agent penetrates into the inside of the treated object and / or adheres to the surface of the treated object.

[0385] Examples

[0386] Hereinafter, the present application will be described in detail by citing examples, but the present application is not limited to these examples.

[0387] Hereinafter, in the case where not particularly described, parts or % or ratio means parts by weight or % by weight or ratio by weight.

[0388] The procedure of the test is described below.

[0389] Spray water-repellency test

[0390] The spray water repellency test was performed in accordance with JIS-L-1092. The spray water repellency test (as shown in Table 1 described below) was expressed in terms of water repellency No.

[0391] A glass funnel having a volume of at least 250 ml and a nozzle capable of spraying 250 ml of water for 20 to 30 seconds was used. The test sheet holder was a metal holder having a diameter of 15 cm. Three test sheet pieces having a size of about 20 cm x 20 cm were prepared, and the pieces were fixed to the test sheet holder so that the pieces were not wrinkled. The center of the spray was placed at the center of the pieces. Room temperature water (250 mL) was put in the glass funnel, and the test sheet pieces were sprayed (for a period of 25 to 30 seconds). The holder was removed from the table, one end of the holder was held, the front surface was set as the lower side, and the opposite end was gently tapped on a hard material. The holder was further rotated by 180°, and the same procedure was repeated, and the excess water drops were removed. In order to evaluate the water repellency in the order of poor to excellent, scores of 0, 50, 70, 80, 90, and 100 were given by comparing the wet test sheet with a wetting comparison standard. The results were obtained from the average of three measurements.

[0392] [Table 1]

[0393]

[0394] Oil-repellency test

[0395] The treated test cloth was stored in a constant temperature and humidity chamber at 21°C and 65% humidity for 4 hours or more. The test solution (shown in Table 2) was also stored at 21°C. The test was performed in a constant temperature and humidity chamber at 21°C and 65% humidity. The test solution was carefully added to the test cloth at 0.05 ml, and after 30 seconds, if the droplet remained on the test cloth, it was determined to pass the test solution. The highest score of the test solution that passed the oil repellency was evaluated in 9 stages of Fail, 1, 2, 3, 4, 5, 6, 7, and 8, from poor to good in oil repellency.

[0396] [Table 2]

[0397]

[0398] Texture

[0399] For the treated PET cloth, the tactile judges determined their differences according to the following criteria. A value of +0.5 indicates an intermediate evaluation.

[0400] 5: significantly softer than untreated cloth

[0401] 4: slightly softer or soft than untreated cloth

[0402] 3: same as untreated cloth

[0403] 2: slightly harder than untreated cloth

[0404] 1: significantly harder than untreated cloth

[0405] Example 1

[0406] A 500-ml reaction flask was charged with CF3CF2-(CF2CF2) n CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7 g, stearyl acrylate 23.4 g, 2-chloroethyl methacrylate 0.4 g, pure water 194 g, water-soluble glycol-based solvent 34.1 g, alkyltrimethylammonium chloride 5.7 g, polyoxyethylene alkyl ether 7.0 g, long-chain alkyl silicone (alkylated silicone wax, melting point 54°C, long-chain alkyl (C 22 CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7 g, stearyl acrylate 23.4 g, 2-chloroethyl methacrylate 0.4 g, pure water 194 g, water-soluble glycol-based solvent 34.1 g, alkyltrimethylammonium chloride 5.7 g, polyoxyethylene alkyl ether 7.0 g, long-chain alkyl silicone (alkylated silicone wax, melting point 54°C, long-chain alkyl (C

[0407] Example 2

[0408] A 500-ml reaction flask was charged with CF3CF2-(CF2CF2) n -CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7 g, stearyl acrylate 23.4 g, 2-chloroethyl methacrylate 0.4 g, pure water 194 g, water-soluble glycol-based solvent 34.1 g, alkyl trimethyl ammonium chloride 5.7 g, polyoxyethylene alkyl ether 7.0 g, vinyl silicone (vinyl content 1.33 mol%, viscosity 500 mm 2 / s (25°C), molecular weight 12000) 59.0 g, and dispersed by ultrasonic emulsification at 60°C for 15 minutes with stirring. After nitrogen replacement in the reaction flask, a solution of water-soluble initiator containing an azo group 0.4 g and water 9 g was added, and the reaction was carried out at 60°C for 20 hours to obtain an aqueous dispersion of a polymer (softener 3). The composition of the polymer was almost the same as that of the added monomers.

[0409] Example 3

[0410] A 500-ml reaction flask was charged with CF3CF2-(CF2CF2) n -CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7 g, stearyl acrylate 23.4 g, 2-chloroethyl methacrylate 0.4 g, pure water 194 g, water-soluble glycol-based solvent 34.1 g, alkyl trimethyl ammonium chloride 5.7 g, polyoxyethylene alkyl ether 7.0 g, vinyl silicone (vinyl content 1.33 mol%, viscosity 500 mm 2 / s (25°C), molecular weight 12000) 59.0 g, and dispersed by ultrasonic emulsification at 60°C for 15 minutes with stirring. After nitrogen replacement in the reaction flask, a solution of water-soluble initiator containing an azo group 0.4 g and water 9 g was added, and the reaction was carried out at 60°C for 20 hours to obtain an aqueous dispersion of a polymer (softener 3). The composition of the polymer was almost the same as that of the added monomers.

[0411] Example 4

[0412] A 500-ml reaction flask was charged with stearyl acrylate 43.2 g, pure water 240 g, tripropylene glycol 27.0 g, stearyl dimethylaminopropylamide 4.0 g, polyoxyethylene isotridecyl ether 7.0 g, acetic acid 0.23 g, long-chain alkyl silicone (alkylated silicone wax, melting point 47°C, long-chain alkyl (C 22Stearate 115.2 g, pure water 240 g, tripropyleneglycol 27.0 g, stearic acid dimethylaminopropylamide 4.0 g, polyoxyethylene isotride ether 7.0 g, acetic acid 0.23 g, were charged in a 500 ml reaction flask, and dispersed with ultrasonic emulsification under stirring at 60°C for 15 minutes. After nitrogen substitution in the reaction flask, a solution of lauryl mercaptan 0.24 g, 2,2-azobis(2-amidinopropane) 2 hydrochloride 0.48 g (hereinafter, referred to as V-50) and water 9 g was added, and the reaction was carried out at 60°C for 5 hours to obtain an aqueous dispersion of the polymer (water repellent 2). The composition of the polymer was almost identical to that of the added monomers.

[0413] Reference Example 1

[0414] A 500 ml reaction flask was charged with CF3CF2-(CF2CF2) n Stearate 115.2 g, pure water 240 g, tripropyleneglycol 27.0 g, stearic acid dimethylaminopropylamide 4.0 g, polyoxyethylene isotride ether 7.0 g, acetic acid 0.23 g, were charged in a 500 ml reaction flask, and dispersed with ultrasonic emulsification under stirring at 60°C for 15 minutes. After nitrogen substitution in the reaction flask, a solution of lauryl mercaptan 0.24 g, 2,2-azobis(2-amidinopropane) 2 hydrochloride 0.48 g (hereinafter, referred to as V-50) and water 9 g was added, and the reaction was carried out at 60°C for 5 hours to obtain an aqueous dispersion of the polymer (water repellent 2). The composition of the polymer was almost identical to that of the added monomers.

[0415] Reference Example 2

[0416] A 500 ml reaction flask was charged with CF3CF2-(CF2CF2)

[0417] Test Example 1

[0418] To water was added the water repellent 1 prepared in Reference Example 1, and then the softener 1 prepared in Example 1 was added to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 2% and a softener effective ingredient concentration (total concentration of the polymer and silicone of the softener) of 2%. A PET cloth, a cotton cloth, and a nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, and were treated with a pin tenter at 170°C for 1 minute by means of a calender. After that, a water repellency test was carried out. The results are shown in Table 3.

[0419] Test Example 2

[0420] To water was added the water repellent 1 prepared in Reference Example 1, and then the softener 2 prepared in Example 2 was added to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 2% and a softener effective ingredient concentration (total concentration of the polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, and were treated at 170°C for 1 minute by means of a pin tenter through a roll. After that, a water repellency test was performed. The results are shown in Table 3.

[0421] Test Example 3

[0422] To water was added the water repellent 1 prepared in Reference Example 1, and then the softener 3 prepared in Example 3 was added to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 2% and a softener effective ingredient concentration (total concentration of the polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, and were treated at 170°C for 1 minute by means of a pin tenter through a roll. After that, a water repellency test was performed. The results are shown in Table 3.

[0423] Test Example 4

[0424] To water was added the water repellent 2 prepared in Reference Example 2, and then the softener 4 prepared in Example 4 was added to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 4% and a softener effective ingredient concentration (total concentration of the polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, and were treated at 170°C for 1 minute by means of a pin tenter through a roll. After that, a water repellency test was performed. The results are shown in Table 3.

[0425] Test Example 5

[0426] To water was added the water repellent 2 prepared in Reference Example 2, and then the softener 4 prepared in Example 4 was added to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 2% and a softener effective ingredient concentration (total concentration of the polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, and were treated at 170°C for 1 minute by means of a pin tenter through a roll. After that, a water repellency test was performed. The results are shown in Table 3.

[0427] Comparative Test Example 1

[0428] To water was added the water repellent 1 prepared in Reference Example 1, to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 4%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll, and treated at 170°C using a pin tenter for 1 minute. After that, a water repellency test was performed. The results are shown in Table 3.

[0429] Comparative Test Example 2

[0430] To water was added the water repellent 1 prepared in Reference Example 1, and then a silicone-based softener commercial product (amino silicone emulsion; weak cationic, solid content 14%, molecular weight of amino silicone 20000) was added, to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 4% and a softener effective ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll, and treated at 170°C using a pin tenter for 1 minute. After that, a water repellency test was performed. The results are shown in Table 3.

[0431] Comparative Test Example 3

[0432] To water was added the water repellent 1 prepared in Reference Example 1, and then a silicone-based softener commercial product (amino silicone emulsion; weak cationic, solid content 14%, molecular weight of amino silicone 20000) was added, to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 2% and a softener effective ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll, and treated at 170°C using a pin tenter for 1 minute. After that, a water repellency test was performed. The results are shown in Table 3.

[0433] Comparative Test Example 4

[0434] To water was added the water repellent 2 prepared in Reference Example 2, to obtain a treatment liquid having a water repellent effective ingredient concentration (polymer concentration of the water repellent) of 4%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll, and treated at 170°C using a pin tenter for 1 minute. After that, a water repellency test was performed. The results are shown in Table 3.

[0435] Comparative Test Example 5

[0436] To water was added the water-repellent agent 2 prepared in Reference Example 2, followed by addition of a silicone-based softening agent commercial product (amino silicone emulsion; weak cationic, solid content 14%, molecular weight of amino silicone 20000) to obtain a treatment liquid having a water-repellent agent effective ingredient concentration (polymer concentration of the water-repellent agent) of 4% and a softening agent effective ingredient concentration (silicone concentration of the softening agent) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll mill, and treated at 170°C using a pin tenter for 1 minute. After that, water-repellency test was performed. The results are shown in Table 3.

[0437] Comparative Test Example 6

[0438] To water was added the water-repellent agent 2 prepared in Reference Example 2, followed by addition of a silicone-based softening agent commercial product (amino silicone emulsion; weak cationic, solid content 14%, molecular weight of amino silicone 20000) to obtain a treatment liquid having a water-repellent agent effective ingredient concentration (polymer concentration of the water-repellent agent) of 2% and a softening agent effective ingredient concentration (silicone concentration of the softening agent) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in the treatment liquid, passed through a roll mill, and treated at 170°C using a pin tenter for 1 minute. After that, water-repellency test was performed. The results are shown in Table 3.

[0439]

[0440] Industrial Applicability

[0441] The softening agent composition of the present application can be used as a softening agent for imparting softness and water repellency to a substrate.

Claims

1. A method for treating a substrate by using a water repellent agent in combination with a softener composition, characterized in that: the softener composition contains: (1) a silicone polymer; (2) a water repellent polymer selected from at least one of a fluorine-containing polymer and a non-fluorine polymer, which is obtained by polymerization in the presence of the silicone polymer; (3) a liquid medium which is water or a mixture of water and an organic solvent; and (4) an emulsifier, the silicone polymer (1) is a polymer represented by the following formula: a is an integer of 0 or more, b is an integer of 0 or more, (a+b) is 5 to 200, the functional group is at least one functional group selected from an epoxy group, an amino group, a vinyl group, a (meth)acrylamide group, a (meth)acrylate group and a hydrocarbon group having 7 to 40 carbon atoms, the fluorine-containing polymer has a repeating unit derived from a fluorine-containing monomer represented by the following formula: a linear or branched aliphatic group having 1 to 20 carbon atoms, an aromatic or cyclic aliphatic group having 6 to 30 carbon atoms, Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, the non-fluorine polymer has a repeating unit derived from a long-chain (meth)acrylic acid monomer represented by the following formula (al): k is 1 to 3, the amount of the silicone polymer is 20 to 88% by weight relative to the total amount of the silicone polymer and the water repellent polymer, wherein the water repellent agent is a fluorine-containing water repellent agent or a non-fluorine water repellent agent, the water repellent polymer is the fluorine-containing polymer when the water repellent agent is the fluorine-containing water repellent agent, and the water repellent polymer is the non-fluorine polymer when the water repellent agent is the non-fluorine water repellent agent.

2. The method for treating a substrate according to claim 1, characterized in that: the non-fluorine polymer is a polymer obtained by polymerization in the presence of the silicone polymer.

3. The method for treating a substrate according to claim 1, characterized in that: the silicone polymer (1) is a polymer represented by the following formula: a is an integer of 0 or more, b is an integer of 0 or more, (a+b) is 5 to 200, the functional group is at least one functional group selected from an epoxy group, an amino group, a vinyl group, a (meth)acrylamide group, a (meth)acrylate group and a hydrocarbon group having 7 to 40 carbon atoms.

4. The method for treating a substrate according to claim 1, characterized in that: the fluorine-containing polymer has a repeating unit derived from a fluorine-containing monomer represented by the following formula: a linear or branched aliphatic group having 1 to 20 carbon atoms, an aromatic or cyclic aliphatic group having 6 to 30 carbon atoms, Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.

5. The method for treating a substrate according to any one of claims 1 to 4, characterized in that: the amount of the silicone polymer (1) is 30 to 88% by weight relative to the total weight of the silicone polymer (1) and the water repellent polymer (2), the amount of the liquid medium (3) is 5 to 99.9% by weight relative to the softener composition, and the amount of the emulsifier (4) is 0.1 to 20 parts by weight relative to 100 parts by weight of the total amount of the silicone polymer (1) and the water repellent polymer (2).

6. The method for treating a substrate according to claim 1, characterized in that: the water repellent polymer (2) further has a repeating unit formed from a non-fluorine non-crosslinking monomer and / or a non-fluorine crosslinking monomer.

7. The method for treating a substrate according to claim 6, characterized in that: the non-fluorine non-crosslinking monomer is a monomer having at least one ethylenic unsaturated double bond. (R 3 -)3Si-O-[-Si(-R 1 )2-O-] a -[-Si(-R 1 )(-X 1 -R 2 )-O-] b -Si(-R 3 )3 wherein R 1 each independently is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, R 2 each independently a functional group, R 3 each independently is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a functional group, X 1 each is a valence bond or a hydrocarbon group having 1 to 10 carbon atoms, 8. The method for treating a substrate according to claim 6, characterized in that: the non-fluorine crosslinking monomer is a compound having at least two ethylenic unsaturated double bonds or a compound having at least one ethylenic unsaturated double bond and at least one reactive group selected from at least one of a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group.

9. The method for treating a substrate according to any one of claims 6 to 8, characterized in that: in the water repellent polymer (2), ​ CH2=C(-X 11 ) -C(=O) -Y 11 -Z 11 -Rf wherein X 11 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX 1 X 2 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX 1 X 2 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; Y 11 is -O- or -NH-; Z 11 is a bond, ​ ​ -R 2 (R 1 )N-SO2- 2 (R 1 )N-CO- 1 R 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, -CH2CH(OR 3 )CH2-(Ar-O) p - wherein R 3 represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar represents an arylene group optionally having a substituent, and p represents 0 or 1, -CH2-Ar-(O) q -CH2-Ar-(O) wherein Ar is an arylene group optionally having a substituent, and q is 0 or 1, or -(CH2) m -SO2-(CH2) n - group or -(CH2) m -S-(CH2) n - group, wherein m is 1 to 10 and n is 0 to 10; ​ ​ CH2=C(-X 21 ) - C(=0) - Y 21 - (R 21 ) k (a1) In formula (a1), R 21 is a hydrocarbon group having 7 to 40 carbon atoms, X 21 is a hydrogen atom, a methyl group or a halogen atom, Y 21 is a group consisting of at least one or more selected from a hydrocarbon group having a carbon number of 1 to 4, -C6H4-, -0-, -C(=0)-, -S(=0)2-, or -NH-, wherein Y 21 is not a hydrocarbon group, ​ ​ ​ ​ ​ ​ ​ ​ Y 21 is a group consisting of at least one or more selected from -CH2-, -CH=, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-, wherein Y 21 is not a hydrocarbon group. ​ In the fluorine-containing monomer, X 11 is a hydrogen atom, a methyl group or a chlorine atom, and Rf has a carbon number of 1 to 6. ​ In the long chain (meth)acrylic monomer, Y 21 -O-, -NH-, -O-C(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -O-C(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -O-C(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -O-(CH2) m -NH-S(=O)2-, -O-(CH2) m -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH-, where m is 1 to 5. ​ ​ ​ ​ ​ ​ ​ Non-fluorine, non-crosslinking monomers in fluoropolymers are of the formula: CH2=CA 21 -C(=O)-Y 21 -A 22 long chain (meth)acrylic monomers, wherein A 21 is a hydrogen atom or a methyl group, A 22 R1is a linear or branched aliphatic hydrocarbon group having 7 to 40 carbon atoms, Y 21 is -O- or -NH-; or The non-fluorine, non-crosslinkable monomer is of the formula: CH2=CA 31 -C(=O)-Y 31 -A 32 The (meth)acrylic monomer containing a cyclic hydrocarbon group is represented by the formula: wherein A 31 is a hydrogen atom or a methyl group, A 32 R1is a cyclic hydrocarbon group having a carbon number of 4 to 20, Y 31 is -O- or -NH-. ​ ​ ​ ​ the total amount of the fluorine-containing monomer and the non-fluorine monomer containing a long-chain hydrocarbon group is 32 to 98% by weight relative to the water-repellent polymer, the amount of the non-fluorine non-crosslinking monomer is 2 to 68% by weight relative to the water-repellent polymer, the amount of the non-fluorine crosslinking monomer is 0.1 to 20 parts by weight relative to 100 parts by weight of the total amount of the fluorine-containing monomer and the non-fluorine monomer containing a long-chain hydrocarbon group.

10. The treatment method of a substrate according to Claim 1, characterized in that: the water-repellent polymer is a fluorine-containing polymer.

11. The treatment method of a substrate according to Claim 1, characterized in that: the water-repellent polymer is a non-fluorine polymer.

12. A substrate, characterized in that: the substrate is a substrate treated by the treatment method according to any one of Claims 1 to 11.

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