Water-repellent softener

Abstract

To provide a softener composition capable of imparting good water repellency and resilience during water-repellent finishing.SOLUTION: A softener composition includes (1) a silicone polymer, (2) a water-repellent polymer, (3) an emulsifier, and (4) water, or a liquid medium which is 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 a silicone polymer. The water-repellent polymer is preferably at least one member selected from the group consisting of fluorine-containing polymers, and non-fluorine polymers.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a softening agent that imparts water repellency and flexibility to a substrate. [Background technology]

[0002] Conventionally, in order to simultaneously impart water-repellent and oil-repellent properties and flexibility to a substrate such as fibers, compositions comprising a perfluoroalkyl group or long-chain alkyl group that imparts water repellency and a modified silicone compound that imparts flexibility have been widely used (for example, Patent Document 1 (JP-A-58-42682), Patent Document 2 (JP-A-60-190408), Patent Document 3 (JP-A-9-143877)). In addition, methods using copolymers of fluorine-containing acrylates and silicone-containing monomers have been proposed for similar purposes (for example, Patent Document 4 (JP-A-02-214791) and Patent Document 5 (JP-A-3-231986)). Patent document 6 (Japanese Patent Publication No. 6-506239) discloses a composition comprising a fluorochemical oligomer portion, an organic portion, and a fluorine-containing compound having a bonding group. Patent document 7 (Japanese Unexamined Patent Publication No. 2001-146548) discloses a composition comprising a perfluoroalkyl group-containing ester and an oligo- or polyurethane. Patent document 8 (Japanese Unexamined Patent Publication No. 2015-531011) discloses a composition comprising an additive and an organopolysiloxane conditioning agent. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 58-42682 [Patent Document 2] Japanese Patent Publication No. 60-190408 [Patent Document 3] Japanese Patent Publication No. 9-143877 [Patent Document 4] Japanese Patent Publication No. 02-214791 [Patent Document 5] Japanese Patent Publication No. 3-231986 [Patent Document 6] Japanese Patent Application Publication No. 6-506239 [Patent Document 7] Japanese Patent Publication No. 2001-146548 [Patent Document 8] Japanese Patent Publication No. 2015-531011 [Overview of the project] [Problems that the invention aims to solve]

[0004] Conventional fabric softeners, when used in combination with water-repellent agents to treat fabrics and other substrates with water-repellent properties, would reduce the water-repellent performance. Furthermore, because fabric softener emulsions and water-repellent emulsions use different emulsion systems, the stability of the emulsion is low in typical mixtures. The purpose of this disclosure is to provide a softening agent composition that can impart good water repellency and flexibility during water-repellent processing. [Means for solving the problem]

[0005] This disclosure is, (1) Silicone polymer, (2) Water-repellent polymer, (3) Emulsifiers, and (4) A liquid medium which is water or a mixture of water and an organic solvent. This relates to a fabric softener composition comprising the above. The water-repellent polymer is preferably produced by polymerizing the monomers constituting the water-repellent polymer in the presence of a silicone polymer. The water-repellent polymer is preferably at least one selected from the group consisting of fluorine-containing polymers and non-fluorine polymers.

[0006] Preferred embodiments of the present invention are as follows: Appearance 1. (1) Silicone polymer, (2) A water-repellent polymer selected from the group consisting of fluorine-containing polymers and non-fluorine polymers, which is polymerized in the presence of a silicone polymer. (3) A liquid medium that is water or a mixture of water and an organic solvent, and (4) An emulsifier comprising a silicone polymer, wherein the amount of the silicone polymer is 20% by weight or more based on the total of the silicone polymer and the water-repellent polymer.

[0007] Aspect 2. The silicone polymer (1) has the formula: (R , , 11 , , 1 , ,

[0008] , , , 11 , , 11 , , -)3Si-O-[-Si(-R 1 )2-O-] a -[-Si(-R 1 )(-X 1 -R 2 )-O-] b -Si(-R 3 )3 [wherein each of R 1 is independently 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, each of R 2 is independently a functional group, each of R 3 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, each of X 1 is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 0 or more, b is an integer of 0 or more, and (a + b) is 5 to 200.] is a polymer represented by The softening agent composition according to Aspect 1, wherein the functional group is at least one functional group selected from the group consisting of 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.

[0008] Aspect 3. The fluorine-containing polymer has the formula: CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [where, X 11 This includes hydrogen atoms, linear or branched alkyl groups having 1 to 21 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and CFX. 1 X 2 Base (however, X 1 and X 2 These are hydrogen atoms, fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms; cyano groups, linear or branched fluoroalkyl groups having 1 to 21 carbon atoms, substituted or unsubstituted benzyl groups, and substituted or unsubstituted phenyl groups; Y 11 is -O- or -NH-; Z 11 Direct coupling, Linear or branched aliphatic groups having 1 to 20 carbon atoms, Aromatic groups or cyclic aliphatic groups having 6 to 30 carbon atoms, formula-R 2 (R 1 )N-SO2- or formula-R 2 (R 1 ) A group represented by N-CO- (wherein R 1 R is an alkyl group having 1 to 10 carbon atoms. 2 This refers to a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms. Formula -CH2CH(OR 3 )CH2-(Ar-O) p -(In the formula, R 3 (where is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group having substituents as needed, and p represents 0 or 1.) Formula -CH2-Ar-(O) q -(wherein Ar is an arylene group which may optionally have substituents, and q is 0 or 1.) or the group represented by -(wherein Ar is an arylene group which may optionally have substituents, and q is 0 or 1.) -(CH2) m -SO2-(CH2) n -Base or -(CH2) m -S-(CH2) n -Based on (where m is between 1 and 10, and n is between 0 and 10); Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. A fluorine-containing polymer having repeating units derived from a fluorine-containing monomer shown, Non-fluorinated polymers, formula: CH2=C(-X 21 )-C(=O)-Y 21 -(R 21 ) k (a1) [In the formula, R 21 It 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 This is a group consisting of at least one selected from divalent to tetravalent carbon-1 hydrocarbon groups (especially -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding hydrocarbon groups), k is between 1 and 3. The softener composition according to embodiment 1 or 2, which is a non-fluorinated polymer having repeating units derived from a long-chain (meth)acrylic monomer represented by .

[0009] Appearance 4. In fluorine-containing monomers, X 11 The fabric softener composition according to embodiment 3, wherein Rf is a hydrogen atom, a methyl group, or a chlorine atom, and the number of carbon atoms of Rf is 1 to 6. Appearance 5. In long-chain (meth)acrylic monomers, Y 21 is -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=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 -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m-C(=O)-O-, -O-(CH2) m -OC(=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 -OC(=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 between 1 and 5.] The fabric softener composition according to embodiment 3.

[0010] Appearance 6. The amount of silicone polymer (1) is 30-90% by weight relative to the total weight of silicone polymer (1) and water-repellent polymer (2). The amount of liquid medium (3) is 5 to 99.9% by weight relative to the softener composition. A softener composition according to any one of embodiments 1 to 5, wherein the amount of emulsifier (4) is 0.1 to 20 parts by weight per 100 parts by weight of the total of silicone polymer (1) and water-repellent polymer (2). Appearance 7. The softener composition according to embodiment 1 or 2, wherein the water-repellent polymer (2) further comprises repeating units formed from a non-fluorine, non-crosslinkable monomer and / or a non-fluorine, crosslinkable monomer.

[0011] Appearance 8. Non-fluorine, non-crosslinkable monomers, In fluorine-containing polymers, formula: CH2=CA 21 -C(=O)-Y 21 -A 22 [In the formula, A 21 is a hydrogen atom or a methyl group, A 22 This is a straight-chain or branched aliphatic hydrocarbon group having 7 to 40 carbon atoms. Y 21 It is -O- or -NH-. It is a long-chain (meth)acrylic monomer represented by, or In fluorine-containing polymers or non-fluorine polymers, the formula is: CH2=CA 31 -C(=O)-Y 31 -A 32 [In the formula, A 31 is a hydrogen atom or a methyl group, A 32 It is a cyclic hydrocarbon group having 4 to 20 carbon atoms. Y 31 It is -O- or -NH-. The softener composition according to embodiment 7, wherein the softener composition is a cyclic hydrocarbon group-containing (meth)acrylic monomer represented by .

[0012] Appearance 9. The softener composition according to embodiment 7, wherein the nonfluorine 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, the reactive group being at least one 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. Appearance 10. In the water-repellent polymer (2), The total amount of fluorine-containing monomers and long-chain hydrocarbon group-containing non-fluorine monomers is 32-98% by weight relative to the water-repellent polymer. The amount of non-fluorine, non-crosslinked monomer is 2 to 68% by weight relative to the water-repellent polymer. A softening agent composition according to any one of embodiments 7 to 9, wherein the amount of non-fluorine crosslinkable monomer is 0.1 to 20 parts by weight per 100 parts by weight of the total of fluorine-containing monomers and long-chain hydrocarbon group-containing non-fluorine monomers.

[0013] Appearance 11. A method for producing a softener composition according to any one of embodiments 1 to 10, comprising polymerizing monomers constituting a water-repellent polymer (2) in the presence of a silicone polymer (1) to produce a water-repellent polymer (2) and obtain a softener composition. Appearance 12. A method for treating a substrate with a softening agent composition according to any one of embodiments 1 to 10. Appearance 13. A substrate treated with a softening agent composition according to any one of embodiments 1 to 10. [Effects of the Invention]

[0014] According to this disclosure, the softening agent composition can impart good flexibility without reducing water repellency, regardless of whether it is a fluorine-containing polymer or a non-fluorine polymer. The fabric softener composition can impart good flexibility without reducing water repellency, unlike conventional fabric softener emulsions that use large amounts of emulsifiers. It can efficiently impart good water and oil repellency along with good flexibility. The fabric softener composition has high emulsion stability. [Modes for carrying out the invention]

[0015] Fabric softener composition, (1) Silicone polymer, (2) Water-repellent polymer, (3) Emulsifiers (surfactants), and (4) A liquid medium which is water or a mixture of water and an organic solvent. The softener composition comprises the following: In the softener composition, the silicone polymer (1) and the water-repellent polymer (2) act as active ingredients.

[0016] (1) Silicone polymer The silicone polymer is a component that mainly imparts flexibility. Generally, the silicone polymer is a linear polymer having a siloxane bond. The silicone polymer preferably has no mercapto group. Generally, the silicone polymer does not react with monomers constituting a water-repellent polymer. The silicone polymer may not have a 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. The silicone polymer has the formula: (R 3 -)3Si-O-[-Si(-R 1 )2-O-] a -[-Si(-R 1 )(-X 1 -R 2 )-O-] b -Si(-R 3 )3 [wherein each of R 1 is independently 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, each of R[[ID=3,4]] 2 is independently a functional group, each of R 3 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, each of X 1 is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, a is an integer of 0 or more, b is an integer of 0 or more, and (a + b) is 5 to 200.] It is preferably a polymer represented by.

[0017] R 1 and R 3In this case, the alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms may be unsubstituted or may be substituted. R 1 and R 3 Specific examples of 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 some or all of the hydrogen atoms bonded to these groups are substituted with a halogen atom, an amino group, a cyano group, etc. R 1 and R 3 are preferably a methyl group or an ethyl group. R 1 and R 3 may have an alkyl group having 3 to 22 carbon atoms or an unsaturated hydrocarbon group having 8 to 40 carbon atoms (for example, a hydrocarbon group having an aromatic ring), but preferably do not have these groups. R 1 and R 3 In, the alkoxy group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxy group having 1 to 4 carbon atoms are a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0018] In terms of being easy to manufacture industrially and being easily available, R 1 and R 3 are preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0019] R 2 is a functional group. R 2 and R 3 In, 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.

[0020] The long-chain hydrocarbon group is preferably a saturated hydrocarbon group having 7 to 40 carbon atoms, for example, 12 to 40, and particularly 23 to 40 carbon atoms. The long-chain hydrocarbon group may be linear or branched, and is preferably an alkyl group. Specific examples of long-chain hydrocarbon groups are the lauryl group (12 carbon atoms), stearyl group (18 carbon atoms), tricosyl group (23 carbon atoms), lignoceryl group (tetracosyl group, 24 carbon atoms), cerotyl group (hexacosyl group, 26 carbon atoms), montyl group (octacosyl group, 28 carbon atoms), merisyl group (triacontane group, 30 carbon atoms), and dotriacontane group (32 carbon atoms).

[0021] X 1 These are directly bonded or divalent hydrocarbon groups with 1 to 10 carbon atoms. Hydrocarbon groups with 1 to 10 carbon atoms include alkylene groups, particularly -(CH2) n - (where n is an integer between 1 and 10, for example, an integer between 1 and 5.) is preferable.

[0022] a is a non-negative integer. In terms of ease of industrial manufacture and availability, a is preferably 40 or less, and more preferably 30 or less. b is an integer greater than or equal to 0, preferably 1 or greater. It is preferable that b is 40 or less, as it is easy to manufacture industrially, readily available, and easy to handle.

[0023] The sum of a and b is between 5 and 200. Preferably, the sum of a and b is between 10 and 100, more preferably between 30 and 80, and particularly more preferably between 40 and 60, in terms of ease of industrial manufacture, availability, and handling. a may be between 0 and 150, for example, 1 and 100. The lower limit of b may be 0, 1, 2, or 3, and the upper limit of b may be 150, 10, or 5.

[0024] Multiple versions of R exist. 1 Group, R 2 Group, R 3 Base and X 1 Each of the elements may be the same or different. R 1Base and R 2 Base and R 3 It is preferable that 50 mol% or more of the total number of groups are methyl groups. The order of existence of the repeating units enclosed by a or b is not limited to the order shown in the chemical formula, but is arbitrary. That is, the silicone polymer may be a random polymer or a block polymer.

[0025] Specific examples of silicone polymers that do not have functional groups are dimethyl silicone and methylphenyl silicone. Silicone polymers preferably have functional groups. Specific examples of silicone polymers having functional groups are as follows: TIFF2023100627000001.tif2964 TIFF2023100627000002.tif2362 TIFF2023100627000003.tif2365 TIFF2023100627000004.tif2371 [In the formula, a represents an integer between 0 and 150, b represents an integer between 1 and 150. (a+b) is between 5 and 200. p is an integer between 0 and 5. n is an integer between 3 and 36, especially between 19 and 36.

[0026] Silicone polymers can be synthesized by conventionally known methods. For example, silicone polymers having long-chain hydrocarbon groups can be obtained, for example, by hydrosilylation of a silicone having SiH groups with an α-olefin (long-chain α-olefin).

[0027] Examples of silicones having SiH groups include methylhydrogensilicone polymers with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, methylhydrogensilicone is preferred because it is easy to manufacture industrially and readily available.

[0028] α-olefins are compounds from which long-chain hydrocarbon groups are derived in silicone polymers. Specific examples of α-olefins include 1-tricosene, 1-tetracosene, 1-hexacosene, 1-octacosene, 1-triaconthene, and 1-dotriaconthene. The hydrosilylation reaction may be carried out by reacting the α-olefin with the SiH group-containing silicone in a stepwise or one-time manner, if necessary, in the presence of a catalyst.

[0029] The amounts of SiH-containing silicone and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent or number-average molecular weight of the SiH-containing silicone.

[0030] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0031] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C. Hydrosilylation reactions are preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction will proceed even without a solvent, but a solvent may be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0032] The weight-average molecular weight (Mw) of silicone polymers is generally between 200 and 100,000, for example, 500 to 50,000, and especially between 1,000 and 20,000. The weight-average molecular weight (Mw) of silicone polymers is generally measured by GPC (gel permeation chromatography) and expressed on a styrene basis.

[0033] The silicone polymer is preferably used in the production of the water-repellent polymer in the form of a liquid or solid (e.g., oil or wax) that does not contain any components other than the silicone polymer. Alternatively, the silicone polymer may be used in the production of the water-repellent polymer in the form of a solution or aqueous emulsion.

[0034] (2) Water-repellent polymer Water-repellent polymers are either fluorine-containing polymers or non-fluorine polymers. Fluorine-containing polymers are polymers having repeating units derived from fluorine-containing monomers having fluoroalkyl groups. Non-fluorine polymers are polymers having repeating units derived from non-fluorine monomers containing long-chain hydrocarbon groups.

[0035] The water-repellent polymers are homopolymers having repeating units derived from fluorine-containing monomers having a fluoroalkyl group or non-fluorine monomers having a hydrocarbon group with 7 to 40 carbon atoms (i.e., long-chain hydrocarbon group-containing non-fluorine monomers), copolymers having repeating units derived from two or more monomers selected from fluorine-containing monomers having a fluoroalkyl group and long-chain hydrocarbon group-containing non-fluorine monomers, or copolymers having repeating units derived from other polymerizable compounds copolymerizable with repeating units derived from fluorine-containing monomers having a fluoroalkyl group or long-chain hydrocarbon group-containing non-fluorine monomers. The water-repellent polymer may be a random polymer or a block polymer.

[0036] The water-repellent polymer (2) may consist only of repeating units derived from (2A) fluorine-containing monomers having a fluoroalkyl group and / or repeating units derived from (2B) long-chain hydrocarbon group-containing nonfluorine monomers, In addition to the repeating units (2A) and / or (2B), (2C) Repeating units derived from non-fluorine, non-crosslinkable monomers and (2D) Repeating units derived from non-fluorine, crosslinkable monomers, either or both. It is preferable that it has

[0037] The water-repellent polymer (2) has repeating units derived from either or both of (2A) a fluorine-containing monomer having a fluoroalkyl group and (2B) a long-chain hydrocarbon group-containing nonfluorine monomer.

[0038] (2A) Fluorine-containing monomer Fluorine-containing monomers are generally polymerizable compounds having a perfluoroalkyl or perfluoroalkenyl group and an acrylic acid group, a methacrylic acid group, or an α-substituted acrylic acid group. Fluorine-containing monomers are generally fluorine-containing acrylic monomers.

[0039] The formula for fluorine-containing monomers is: CH2=C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [where, X 11 is a hydrogen atom, a monovalent organic group, or a halogen atom. Y 11 is -O- or -NH-, Z 11 These are directly bonded or divalent organic groups, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. It is preferable that the compound is one of the compounds represented by (acrylate ester or acrylamide).

[0040] X 11This includes hydrogen atoms, linear or branched alkyl groups having 1 to 21 carbon atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, and CFX. 1 X 2 Base (however, X 1 and X 2 This is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. It may also be a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. X 11 Specific examples include H, CH3, Cl, Br, I, F, CN, and CF3. 11 Preferably, this is a hydrogen atom, a methyl group, or a chlorine atom.

[0041] Y 11 It is preferable that it be -O-.

[0042] Z 11 For example, a linear or branched aliphatic group having 1 to 20 carbon atoms (especially an alkylene group), e.g., formula -(CH2) x - (where x is between 1 and 10) is the base represented by equation -R 2 (R 1 )N-SO2- or formula-R 2 (R 1 ) A group represented by N-CO- (wherein R 1 R is an alkyl group having 1 to 10 carbon atoms. 2 This is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms. ) or formula -CH2CH(OR 3 )CH2-(Ar-O) p -(In the formula, R 3 ) is a hydrogen atom, or an acyl group having 1 to 10 carbon atoms (e.g., formyl or acetyl), Ar is an arylene group with substituents as needed, and p represents 0 or 1. ) or a group represented by the formula -CH2-Ar-(O) q -(wherein Ar is an arylene group optionally substituted, and q is 0 or 1.) -(CH2) m -SO2-(CH2) n -Base or -(CH2)m -S-(CH2) n -The base may be (where m is between 1 and 10, and n is between 0 and 10).

[0043] Z 11 This includes aliphatic groups with 1 to 10 carbon atoms, aromatic or cyclic aliphatic groups with 6 to 18 carbon atoms, and -CH2CH2N(R 1 )SO2- group (however, R 1 (This refers to an alkyl group having 1 to 4 carbon atoms.) -CH2CH(OZ 1 )CH2-(Ph-O) p -Base (however, Z 1 is a hydrogen atom or acetyl group, Ph is a phenylene group, and p is 0 or 1. ), -(CH2) n -Ph-O- group (where Ph is a phenylene group and n is 0-10), -(CH2) m -SO2-(CH2) n -Base or -(CH2) m -S-(CH2) n -The group is preferably a - group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly with 1 to 4 carbon atoms, for example 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or SO2 group may be directly bonded to the Rf group.

[0044] The Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6, and especially 6. Examples of Rf groups 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 so on.

[0045] Specific examples of fluorine-containing monomers include, but are not limited to, the following. CH2=C(-H)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-C6H4-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3) SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5) SO2-Rf CH2=C(-H)-C(=O)-O-CH2CH(-OH) CH2-Rf

[0046] CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3) CH2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-H)-C(=O)-NH-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf

[0047] CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf

[0048] CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf

[0049] CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-F)-C(=O)-NH-(CH2)3-Rf

[0050] CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf

[0051] CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf [In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.]

[0052] (2B) Long-chain hydrocarbon group-containing nonfluorine monomer Long-chain hydrocarbon group-containing non-fluorinated monomers do not contain fluoroalkyl groups. Long-chain hydrocarbon group-containing non-fluorinated monomers do not contain fluorine atoms. The number of carbon atoms in the long-chain hydrocarbon group is preferably 7 to 40, for example 10 to 40, particularly 12 to 30, and especially 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. Long-chain hydrocarbon group-containing nonfluorine monomers are generally nonfluorine acrylic monomers having long-chain hydrocarbon groups.

[0053] The long-chain hydrocarbon group-containing nonfluorine monomer (2B) is given by formula: CH2=C(-X 21 )-C(=O)-Y 21 -(R 21 ) k (a1) [In the formula, R 21 It 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 This is a group consisting of at least one selected from divalent or trivalent to tetravalent carbon-1 hydrocarbon groups (especially -CH2-, -CH=), -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding hydrocarbon groups), k is between 1 and 3. A monomer represented by [the specified formula] is preferred, particularly a (meth)acrylic monomer.

[0054] Y 21 It is a divalent to tetravalent group. 21 The group is preferably divalent or trivalent, and particularly preferably divalent. Y 21 This group may consist of at least one carbon-1 hydrocarbon group, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH- (excluding hydrocarbon groups). Examples of carbon-1 hydrocarbon groups include -CH2-, -CH= with a branched structure, or -C≡ with a branched structure.

[0055] Y 21 -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'- [In the formula, Y' is a direct bond, -O-, -NH- or -S(=O)2-, R' is -(CH2) m -(m is an integer between 1 and 5) or -C6H4- (phenylene group). That's fine.

[0056] Y 21 Specific examples are -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=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 -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=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 -OC(=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 The formula is -S(=O)2-NH- [where m is 1 to 5, especially 2 or 4].

[0057] Y 21 When is divalent, k is 1, and Y 21 When is trivalent, k is 2, and Y 21 When the compound is tetravalent, k is 3.

[0058] Examples of acrylic monomers having long-chain hydrocarbon groups are: formula: CH2=C(-X 24 )-C(=O)-Y 22 -R 22 (a2) [In the formula, R 22 It is a hydrocarbon group having 7 to 40 carbon atoms. X 24 is a hydrogen atom, a methyl group, or a halogen atom, Y 22 It is -O- or -NH-. Acrylic monomers represented by, and formula: CH2=C(-X 25 )-C(=O)-Y 23 -Z(-Y 24 -R 23 ) m (a3) [In the formula, R 23 It is a hydrocarbon group having 7 to 40 carbon atoms. X 25 is a hydrogen atom, a methyl group, or a halogen atom, Y 23is -O- or -NH-, Y 24 These are -OC(=O)-NH-, -NH-C(=O)-O-, or -NH-C(=O)-NH-, Z is a divalent or trivalent hydrocarbon group with 1 to 5 carbon atoms. m is either 1 or 2. It is a urethane monomer represented by [the symbol].

[0059] In this specification, urethane monomers also include urea monomers having a urea group. Urethane monomer (a3) ​​can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of alkyl groups in hydroxyalkyl (meth)acrylate and hydroxyalkyl (meth)acrylamide include alkyl groups having 2 to 10 carbon atoms, such as ethyl, propyl, butyl, hexane, and decane groups. Examples of long-chain alkyl isocyanates include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate. Alternatively, the urethane monomer (a3) ​​can also be produced by reacting a (meth)acrylate having an isocyanate group in its side chain, such as 2-methacryloyloxyethyl isocyanate, with a long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkyl alcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0060] Preferred examples of long-chain alkyl group-containing acrylic monomers are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl α-chloroacrylate, behenyl α-chloroacrylate; Stearyl(meth)acrylamide, behenyl(meth)acrylamide;

[0061] TIFF2023100627000005.tif2453

[0062] TIFF2023100627000006.tif2152 TIFF2023100627000007.tif2253 TIFF2023100627000008.tif2153

[0063] TIFF2023100627000009.tif2254 TIFF2023100627000010.tif2154 TIFF2023100627000011.tif2155

[0064] TIFF2023100627000012.tif2152 TIFF2023100627000013.tif2157 TIFF2023100627000014.tif2864 TIFF2023100627000015.tif2866

[0065] TIFF2023100627000016.tif2045 TIFF2023100627000017.tif2045 [In the above formula, m is a number between 1 and 5, and n is a number between 7 and 40.] The compound with the above chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may include a methacle compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom.

[0066] It is preferable that the long-chain hydrocarbon group-containing nonfluorine monomer (2B) has a melting point of 10°C or higher, more preferably 25°C or higher.

[0067] As a long-chain hydrocarbon group-containing nonfluorine monomer (2B), X 21 , X 24 and X 25 It is preferable that the atom is a hydrogen atom and that it is an acrylate, and in particular, stearyl acrylate is preferred.

[0068] The water-repellent polymer (2) has repeating units (2A) and / or (2B) (i.e., repeating units derived from monomers (2A) and / or (2B)), (2C) Repeating units derived from non-fluorine, non-crosslinkable monomers and (2D) Repeating units derived from non-fluorine, crosslinkable monomers, either or both. It is preferable that it has

[0069] (2C) Non-fluorine, non-crosslinkable monomer Non-fluorinated, non-crosslinkable monomers (2C) are monomers other than long-chain hydrocarbon group-containing non-fluorinated monomers (2B). Non-fluorinated, non-crosslinkable monomers (2C) are monomers that do not contain fluorine atoms. Non-fluorinated, non-crosslinkable monomers (2C) do not have crosslinkable functional groups. Unlike crosslinkable monomers (2D), non-fluorinated, non-crosslinkable monomers (2C) are non-crosslinkable. Non-fluorinated, non-crosslinkable monomers (2C) are preferably non-fluorinated monomers having a carbon-carbon double bond. Non-fluorinated, non-crosslinkable monomers (2C) are preferably vinyl monomers that do not contain fluorine. Non-fluorinated, non-crosslinkable monomers (2C) are generally compounds having one carbon-carbon double bond.

[0070] A preferred non-fluorine, non-crosslinkable monomer (2C) is given by formula: CH2=CA-T [In the formula, A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, and an iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 40 carbon atoms, or a chain or cyclic organic group having 1 to 41 carbon atoms and possessing an ester bond. It is a compound represented by [the formula shown].

[0071] Examples of chain-like or cyclic hydrocarbon groups having 1 to 40 carbon atoms include straight-chain or branched aliphatic hydrocarbon groups having 1 to 40 carbon atoms, cyclic aliphatic groups having 4 to 40 carbon atoms, aromatic hydrocarbon groups having 6 to 40 carbon atoms, and aromatic aliphatic hydrocarbon groups having 7 to 40 carbon atoms.

[0072] Examples of linear or cyclic organic groups having 1 to 41 carbon atoms and containing ester bonds are -C(=O)-OQ and -OC(=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, and an aromatic aliphatic hydrocarbon group having 7 to 40 carbon atoms).

[0073] Preferred examples of non-fluorinated, non-crosslinked monomers (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 ethers. Non-fluorinated, non-crosslinked monomers (2C) are not limited to these examples.

[0074] The nonfluorine, non-crosslinked monomer (2C) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1 to 17, for example, 1 to 10. For example, the nonfluorine, non-crosslinked monomer (2C) may have the general formula: CH2=CA 1 COOA 2 [In the formula, A 1 This is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (e.g., a chlorine atom, a bromine atom, and an iodine atom). A 2 C n H 2n+1 This is an alkyl group represented by (n=1~17). It may be an acrylate as shown. The fluorine-containing monomer does not necessarily have to have repeating units derived from (meth)acrylate esters having an alkyl group with 1 to 17 carbon atoms.

[0075] The non-fluorine, non-crosslinked monomer (2C) may be a (meth)acrylate monomer having a cyclic hydrocarbon group. The (meth)acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth)acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth)acrylate group are directly bonded. Examples of cyclic hydrocarbon groups include monocyclic groups, polycyclic groups, and crosslinked ring groups, which may be saturated or unsaturated. It is preferable that the cyclic hydrocarbon group is saturated. It is preferable that the number of carbon atoms in the cyclic hydrocarbon group is 4 to 20. Examples of cyclic hydrocarbon groups include cyclic aliphatic groups with 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, aromatic groups with 6 to 20 carbon atoms, and aromatic aliphatic groups with 7 to 20 carbon atoms. It is particularly preferable that the number of carbon atoms in the cyclic hydrocarbon group is 15 or less, for example, 10 or less. It is preferable that the carbon atoms in the ring of the cyclic hydrocarbon group are directly bonded to the ester group in the (meth)acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

[0076] Specific examples of cyclic hydrocarbon groups include cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but a methacrylate group is particularly preferred. Specific examples of monomers having cyclic hydrocarbon groups include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate.

[0077] The non-fluorine, non-crosslinked monomer (2C) may be a halogenated olefin. The halogenated olefin may be a C2-C20 halogenated olefin substituted with 1-10 chlorine atoms, bromine atoms, or iodine atoms. The halogenated olefin is preferably a C2-C20 chlorinated olefin, and more preferably a C2-C5 olefin having 1-5 chlorine atoms. Preferred specific examples of halogenated olefins are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

[0078] (2D) Non-fluorine crosslinkable monomer The water-repellent polymer may have repeating units derived from a non-fluorinated crosslinkable monomer (2D). The non-fluorinated crosslinkable monomer (2D) is a monomer that does not contain fluorine atoms. The non-fluorinated crosslinkable monomer (2D) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorinated crosslinkable monomer (2D) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups include hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, etc.

[0079] Examples of non-fluorinated crosslinkable monomers (2D) include, but are not limited to, diacetone acrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, etc.

[0080] By copolymerizing a non-fluorine, non-crosslinked monomer (2C) and / or a non-fluorine, crosslinked monomer (2D), various properties such as water and oil repellency, stain resistance, and their cleaning resistance, washability, solvent solubility, hardness, and feel can be improved as needed.

[0081] Monomers (2A), (2B), (2C), and (2D) are prepared and polymerized in the presence of silicone polymer (1) to obtain water-repellent polymer (2).

[0082] Although not bound by theory, it is thought that the water-repellent polymer (2) and the silicone polymer (1) form identical particles in the emulsion.

[0083] The amount of silicone polymer (1) may be 20 to 95% by weight, for example 30 to 90% by weight, and particularly 40 to 88% by weight, relative to the total weight of silicone polymer (1) and water-repellent polymer (2). The amount of silicone polymer (1) may be 51% or more by weight, for example 55% or more by weight. The amount of water-repellent polymer (2) may be 5 to 80% by weight, for example 10 to 70% by weight, and particularly 12 to 60% by weight, relative to the total weight of silicone polymer (1) and water-repellent polymer (2).

[0084] Each of the monomers (2A), (2B), (2C), and (2D) may be a single type or a combination of two or more types.

[0085] The respective amounts of the fluorine-containing monomer (2A) and the long-chain hydrocarbon group-containing nonfluorine monomer (2B) (or the total of monomers (2A) and monomer (2B)) (where the total of monomers (2A) and monomer (2B) is 100% by weight or less) may be 30 to 100% by weight, preferably 32 to 98% by weight, for example 35 to 95% by weight, and particularly 40 to 90% by weight, relative to the water-repellent polymer. In a water-repellent polymer, either a fluorine-containing monomer (2A) or a long-chain hydrocarbon group-containing nonfluorine monomer (2B) may be present alone, or both a fluorine-containing monomer (2A) and a long-chain hydrocarbon group-containing nonfluorine monomer (2B) may be present in the water-repellent polymer. When both a fluorine-containing monomer (2A) and a long-chain hydrocarbon group-containing nonfluorine monomer (2B) are present in the water-repellent polymer, the amount of the fluorine-containing monomer (2A) may be 10 to 90% by weight, for example, 30 to 70% or 25 to 49%, relative to the total amount of monomers (2A) and monomers (2B).

[0086] In a water-repellent polymer, with respect to 100 parts by weight of a total of fluorine-containing monomer (2A) and long-chain hydrocarbon group-containing non-fluorine monomer (2B), The amount of non-fluorine, non-crosslinkable monomer (2C) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, and especially 1 to 200 parts by weight. The amount of non-fluorine crosslinkable monomer (2D) may be 50 parts by weight or less, for example, 30 parts by weight or less, and particularly 0.1 to 20 parts by weight. The amount of non-fluorine, non-crosslinkable monomer (2C) may be 2 to 68% by weight, for example, 5 to 65% by weight, and particularly 10 to 60% by weight, relative to the water-repellent polymer (or the sum of monomers (2A), monomer (2B), and monomer (2C)).

[0087] The weight-average molecular weight (Mw) of a water-repellent polymer is generally between 1,000 and 1,000,000, for example, 2,000 to 500,000, and particularly between 3,000 and 200,000. The weight-average molecular weight (Mw) of a water-repellent polymer is generally measured by GPC (gel permeation chromatography) and expressed on a styrene basis.

[0088] (3) Liquid media The softening agent composition contains a liquid medium. The liquid medium may be an organic solvent, but is preferably water or a mixture of water and an organic solvent. Fabric softener compositions are generally solutions or dispersions. A solution is a solution in which the polymer is dissolved in an organic solvent. A 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).

[0089] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The liquid medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of organic solvent may be 30% by weight or less, for example, 10% by weight or less (preferably 0.1% by weight or more), relative to the liquid medium. It is preferable that the liquid medium be water alone. The amount of liquid medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, relative to the softener composition.

[0090] (4) Emulsifier (surfactant) Generally, fabric softener compositions are aqueous dispersions. Fabric softener compositions contain emulsifiers (surfactants). If the silicone polymer is in the form of an aqueous dispersion before manufacturing the softener composition, it is preferable that the aqueous dispersion contains a surfactant. In a fabric softener composition, the surfactant includes a nonionic surfactant. Furthermore, the surfactant may include one or more surfactants selected from cationic surfactants, anionic surfactants, and amphoteric surfactants. The surfactant may consist solely of a nonionic surfactant, or it may be a combination of a nonionic surfactant and a cationic surfactant.

[0091] (4A) Nonionic surfactant Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides. Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0092] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 10-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms. Examples of ester ethers are compounds formed by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are 1-6 valent (especially 2-5 valent) alcohols with 1-50 carbon atoms (especially 3-30 carbon atoms) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2-50 carbon atoms, especially 5-30 carbon atoms.

[0093] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolamides. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups. Polyhydric alcohols may be divalent to pentavalent alcohols with 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (a secondary amine or preferably a tertiary amine) (for example, having 5 to 50 carbon atoms).

[0094] The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. In general, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100. Nonionic surfactants are selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and are preferably nonionic surfactants having an oxyalkylene group.

[0095] Nonionic surfactants may be alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, polyalkylene glycol esters of linear and / or branched fatty acids (saturated and / or unsaturated), polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, etc. Among these, those in which the structure of the alkylene oxide adduct and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (which may be random copolymers or block copolymers) are preferred. Furthermore, nonionic surfactants are preferable because they do not contain aromatic groups due to environmental concerns (biodegradability, endocrine disruptors, etc.).

[0096] Nonionic surfactants are defined by the formula: R 1 O-(CH2CH2O) p -(R 2 O) q -R 3 [In the formula, R 1 This is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. R 2 Each of these is independently identical or distinct, an alkylene group having 3 or more carbon atoms (e.g., 3 to 10). R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by

[0097] R 1 is preferably 8 to 20, particularly 10 to 18 carbon atoms. R 1 Preferred specific examples of include lauryl group, tridecyl group, oleyl group. R 2 Examples of are propylene group, butylene group. In the nonionic surfactant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain. The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly, a polyoxyalkylene chain) in the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, etc., and among them, an oxypropylene chain is preferred.

[0098] Specific examples of the nonionic surfactant include condensation products with ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C7-C 19 ) or alkyl (C 12 -C 18 ) amine, etc.

[0099] 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, based on the molecular weight of the nonionic surfactant (copolymer). The average molecular weight of the nonionic surfactant is generally from 300 to 5,000, for example, from 500 to 3,000. The nonionic surfactant may be a single kind or a mixture of two or more kinds.

[0100] (4B) Cationic surfactant The cationic surfactant is preferably a compound having no amide group.

[0101] The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene-added ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt type surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride.

[0102] Preferred examples of the cationic surfactant are R 21 -N + (-R 22 )(-R 23 )(-R 24 ) X - [In the formula, R 21 , R 22 , R <00002​​​​​​​​​​​​​​​​​​The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0103] The cationic surfactant is preferably an ammonium salt. The cationic surfactant has the formula: R 1 p - N + R 2 q X - [In the formula, R 1 is C12 or higher (for example, C 12 ~C 50 ) linear and / or branched aliphatic (saturated and / or unsaturated) groups, R 2 These are H or C1-C4 alkyl groups, benzyl groups, and polyoxyethylene groups (number of oxyethylene groups e.g., 1 (especially 2, especially 3) to 50). (CH3 and C2H5 are particularly preferred.) X is a halogen atom (e.g., a chlorine atom), a C1-C4 fatty acid base, p is either 1 or 2, q is either 2 or 3, and p + q = 4. It may be an ammonium salt represented by R. 1 The number of carbon atoms can be 12 to 50, for example, 12 to 30.

[0104] Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0105] Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.

[0106] The amount of emulsifier (4) may be 0.1 to 20 parts by weight, for example, 1 to 10 parts by weight, per 100 parts by weight of the total of silicone polymer (1) and water-repellent polymer (3). Nonionic surfactants, cationic surfactants, and amphoteric surfactants may each be one type or a combination of two or more. The amount of cationic surfactant may be 5% by weight or more, preferably 10% by weight or more, and more preferably 20% by weight or more, relative to the total amount of surfactant. The weight ratio of nonionic surfactant to cationic surfactant is preferably 95:5 to 20:80, and more preferably 85:15 to 40:60. The amount of cationic surfactant may be 0.05 to 10 parts by weight, for example, 0.1 to 8 parts by weight, per 100 parts by weight of polymer. The total amount of surfactant may be 0.1 to 20 parts by weight, for example, 0.2 to 10 parts by weight, per 100 parts by weight of polymer.

[0107] (5) Other ingredients The surface treatment agent may contain additives as components other than silicone polymers, water-repellent polymers, liquid media, and surfactants. Examples of additives include silicon-containing compounds, waxes, and acrylic emulsions. Other examples of additives include drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture modifiers, slipperiness modifiers, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insecticides, fragrances, and flame retardants.

[0108] Generally, a softener composition can be produced by adding monomers constituting a water-repellent polymer, a surfactant, water, and optionally an organic solvent to a silicone polymer (silicone oil or silicone wax), which is preferably in the form of an oil or wax, and then polymerizing the monomers.

[0109] The softener composition is preferably manufactured by emulsion polymerization. Alternatively, solution polymerization or suspension polymerization may be used.

[0110] In emulsion polymerization, monomers are emulsified in water in the presence of a polymerization initiator and a surfactant (emulsifier), and then polymerized by stirring at a temperature of 50-80°C for 1-10 hours after nitrogen purging. Polymerization initiators include water-soluble ones such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble ones such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. The polymerization initiator is used in an amount of 0.01 to 10 parts by weight per 100 parts by weight of monomer.

[0111] To obtain a polymer aqueous dispersion with excellent stability during storage, it is desirable to polymerize the monomers by micronizing them in water using an emulsifying device that can impart strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. Various emulsifiers, including anionic, cationic, and nonionic types, can be used as emulsifiers, typically in an amount ranging from 0.5 to 20 parts by weight per 100 parts by weight of monomer. It is preferable to use anionic and / or nonionic and / or cationic emulsifiers. If the monomers are not completely miscible, it is preferable to add a compatibilizer that allows them to be sufficiently miscible, such as a water-soluble organic solvent or a low molecular weight monomer. Adding a compatibilizer can improve emulsification and copolymerization properties.

[0112] Examples of water-soluble organic solvents include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, and ethanol, and they may be used in amounts of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of water. Examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, and they may be used in amounts of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, per 100 parts by weight of the total amount of monomers.

[0113] In polymerization, chain transfer agents may be used. The molecular weight of the polymer can be changed depending on the amount of chain transfer agent used. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially alkyl mercaptans (e.g., with 1 to 40 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. The amount of chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, per 100 parts by weight of the total amount of monomers.

[0114] The softening agent composition (treatment agent) may be in the form of a solution, emulsion or aerosol. The softening agent composition is preferably an aqueous dispersion. The softening agent composition comprises a silicone polymer and a water-repellent polymer (active components of the softening agent composition) and a medium (particularly, a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the treatment agent. In the treatment agent, the total concentration of the silicone polymer and the water-repellent polymer may be 0.01 to 95% by weight, 0.1 to 60% by weight, for example 5 to 50% by weight.

[0115] The softening agent composition can be applied to the object to be treated by a conventionally known method. Usually, the treatment agent is dispersed and diluted in an organic solvent or water, and a method of attaching it to the surface of the object to be treated and drying it by a known method such as dip coating, spray coating, foam coating, etc. is adopted. Also, if necessary, it may be applied together with a suitable crosslinking agent (for example, blocked isocyanate) and cured. Furthermore, it is also possible to add and use together with the treatment agent of the present disclosure an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. The total concentration of the silicone polymer and the water-repellent polymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

[0116] Examples of the object to be treated with the softening agent composition (treatment agent) include textile products, stone, filters (for example, electrostatic filters), dust masks, parts of fuel cells (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plasters. Various examples can be given as textile products. For example, animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof.

[0117] Textile products may be in any form, such as fibers or cloth.

[0118] The softening agent composition (or silicone polymer and water-repellent polymer) can be applied to a fibrous substrate (e.g., a textile product) by any known method for treating textile products in liquid. When the textile product is a cloth, the cloth may be immersed in the treatment agent, or the treatment agent may be applied to or sprayed onto the cloth. The treated textile product is dried, preferably heated, for example, at 100°C to 200°C, to develop oil-repellent properties.

[0119] Alternatively, the fabric softener composition may be applied to textile products by cleaning methods, for example, by washing or dry cleaning.

[0120] The textile products to be processed are typically cloths, including woven, knitted and nonwoven fabrics, cloths in garment form and carpets, but may also be fibers or yarns or intermediate textile products (e.g., slivers or rovings). The textile material may be natural fibers (e.g., cotton or wool), chemical fibers (e.g., viscose rayon or reocell), or synthetic fibers (e.g., polyester, polyamide or acrylic fibers), or a mixture of fibers (e.g., a mixture of natural and synthetic fibers). The softening composition is particularly effective in making cellulosic fibers (e.g., cotton or rayon) oleophobic and oil-repellent. The method of this disclosure also generally makes textile products hydrophobic and water-repellent.

[0121] Alternatively, the fibrous substrate may be leather. The softening composition may be applied to the leather in the form of an aqueous solution or aqueous emulsion at various stages of leather processing, for example, during the wetting process or during the finishing process, in order to make the leather hydrophobic and oleophobic. Alternatively, the fibrous substrate may be paper. The softening agent composition may be applied to pre-formed paper, or it may be applied at various stages of papermaking, for example, during the drying period of the paper.

[0122] The fabric softener composition can impart oil repellency to the treated object. The improvement in oil repellency is particularly noticeable when the fabric softener composition is used together with a water-repellent fluorine-containing polymer.

[0123] "Treatment" refers to applying a treatment agent to an object to be treated by means of immersion, spraying, coating, etc. Through treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated. [Examples]

[0124] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. In the following, parts, percentages, or ratios refer to parts by weight, weight percentages, or weight ratios, unless otherwise specified. The examination procedure is as follows:

[0125] Shower water repellency test A shower water repellency test was conducted in accordance with JIS-L-1092. The shower water repellency test results are expressed by a water repellency number (as shown in Table 1 below). Use a glass funnel with a volume of at least 250 ml and a spray nozzle capable of spraying 250 ml of water for 20 to 30 seconds. The specimen frame is a metal frame with a diameter of 15 cm. Prepare three specimen sheets, each approximately 20 cm x 20 cm in size, and secure the sheets to the specimen holder frame, ensuring they are wrinkle-free. Position the spray center at the center of the sheet. Pour 250 ml of room temperature water into the glass funnel and spray it onto the specimen sheets (for 25 to 30 seconds). Remove the holding frame from the stand, grasp one end of the holding frame with the front surface facing downwards, and lightly tap the opposite end with a hard object. Rotate the holding frame another 180° and repeat the same procedure to remove excess water droplets. Compare the wet specimens to a wet comparison standard to assign scores from 0, 50, 70, 80, 90, and 100, ranging from poor to excellent water repellency. Obtain the results from the average of three measurements.

[0126] [Table 1]

[0127] Oil repellency test The treated test cloth is stored in a constant temperature and humidity chamber at 21°C and 65% humidity for at least 4 hours. The test solution (shown in Table 2) is also stored at 21°C. The test is conducted in a constant temperature and humidity chamber at 21°C and 65% humidity. 0.05 ml of the test solution is gently dropped onto the test cloth, and after 30 seconds, if the droplet remains on the test cloth, the test solution is considered to have passed. Oil repellency is evaluated on a 9-point scale from Fail, 1, 2, 3, 4, 5, 6, 7, and 8, with the highest score for a passing test solution being used.

[0128] [Table 2]

[0129] texture The differences in the treated PET fabric were assessed by touch according to the following criteria. An additional value of 0.5 indicates an intermediate evaluation. 5: Significantly softer than untreated fabric. 4: Untreated fabric and slightly or softened 3: Same as untreated fabric 2: Slightly harder than untreated 1: Significantly harder than untreated material.

[0130] Example 1 CF3CF2-(CF2CF2) in a 500ml reaction flask n -CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7g, stearyl acrylate 23.4g, 2-chloroethyl methacrylate 0.4g, pure water 194g, water-soluble glycol solvent 34.1g, alkyltrimethylammonium chloride 5.7g, polyoxyethylene alkyl ether 7.0g, long-chain alkyl silicone (alkylated silicone wax, melting point 54℃, long-chain alkyl (C) 22 59.0 g of alkyl group (60% content, molecular weight 8000) was added and emulsified and dispersed under ultrasonic waves at 60°C for 15 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 0.4 g of azo group-containing water-soluble initiator and 9 g of water was added and the mixture was reacted at 60°C for 20 hours to obtain an aqueous dispersion of the polymer (softener 1). The composition of the polymer was almost identical to the composition of the starting monomer.

[0131] Example 2 CF3CF2-(CF2CF2) in a 500ml reaction flask n -CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7g, stearyl acrylate 23.4g, 2-chloroethyl methacrylate 0.4g, pure water 194g, water-soluble glycol solvent 34.1g, alkyltrimethylammonium chloride 5.7g, polyoxyethylene alkyl ether 7.0g, epoxy silicone (epoxy group functional group equivalent 530g / mol, viscosity 50mm) 259.0 g of (25°C, molecular weight 10000) was added and emulsified and dispersed under ultrasonic waves at 60°C for 15 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 0.4 g of azo group-containing water-soluble initiator and 9 g of water was added and reacted at 60°C for 20 hours to obtain an aqueous dispersion of the polymer (softener 2). The composition of the polymer was almost identical to the composition of the starting monomer.

[0132] Example 3 CF3CF2-(CF2CF2) in a 500ml reaction flask n -CH2CH2OCOC(Cl)=CH2(n=2.0) 19.7g, stearyl acrylate 23.4g, 2-chloroethyl methacrylate 0.4g, pure water 194g, water-soluble glycol solvent 34.1g, alkyltrimethylammonium chloride 5.7g, polyoxyethylene alkyl ether 7.0g, vinyl silicone (vinyl group content 1.33mol%, viscosity 500mm) 2 59.0 g of (molecular weight 12000) was added and emulsified and dispersed by ultrasound at 60°C for 15 minutes under stirring. After purging the reaction flask with nitrogen, a solution of 0.4 g of azo group-containing water-soluble initiator and 9 g of water was added and the mixture was reacted at 60°C for 20 hours to obtain an aqueous dispersion of the polymer (softener 3). The composition of the polymer was almost identical to the composition of the starting monomer.

[0133] Example 4 In a 500ml reaction flask, combine 43.2g stearyl acrylate, 240g pure water, 27.0g tripropylene glycol, 4.0g dimethylaminopropyl stearate, 7.0g polyoxyethylene isotridecyl ether, 0.23g acetic acid, and long-chain alkyl silicone (alkylated silicone wax, melting point 47°C, long-chain alkyl (C)). 22 72 g of alkyl group (60% content, molecular weight 8000) was added and emulsified and dispersed by ultrasound at 60°C for 15 minutes under stirring. After purging the reaction flask with nitrogen, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis(2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added and reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer (softener 4). The composition of the polymer was almost identical to the composition of the starting monomer.

[0134] Reference example 1 CF3CF2-(CF2CF2) in a 500ml reaction flask n -CH2CH2OCOC(Cl)=CH2(n=2.0) 46.1g, stearyl acrylate 56.2g, 2-chloroethyl methacrylate 2.0g, pure water 194g, water-soluble glycol solvent 34.1g, alkyltrimethylammonium chloride 5.7g, and polyoxyethylene alkyl ether 7.0g were added and the mixture was emulsified and dispersed by sonication at 60°C for 15 minutes under stirring. After purging the reaction flask with nitrogen, a solution of azo group-containing water-soluble initiator 0.4g and water 9g was added and the mixture was reacted at 60°C for 20 hours to obtain an aqueous dispersion of the polymer (water repellent 1). The composition of the polymer was almost identical to the composition of the starting monomer.

[0135] Reference example 2 In a 500 ml reaction flask, 115.2 g of stearyl acrylate, 240 g of pure water, 27.0 g of tripropylene glycol, 4.0 g of dimethylaminopropyl stearate, 7.0 g of polyoxyethylene isotridecyl ether, and 0.23 g of acetic acid were added, and the mixture was emulsified and dispersed under sonication at 60°C for 15 minutes with stirring. After purging the reaction flask with nitrogen, a solution of 0.24 g of lauryl mercaptan, 0.48 g of 2,2-azobis(2-amidinopropane) 2-hydrochloride (hereinafter referred to as V-50), and 9 g of water was added, and the mixture was reacted 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 the composition of the starting monomer.

[0136] Test Example 1 Water was mixed with water to obtain a treatment solution with a water repellent 1 prepared in Reference Example 1, followed by a softener 1 prepared in Example 1. The water repellent active ingredient concentration (polymer concentration of the water repellent) was 2%, and the softener active ingredient concentration (total concentration of polymer and silicone of the softener) was 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0137] Test Example 2 Water was mixed with water repellent 1, prepared in Reference Example 1, and then softener 2, prepared in Example 2, to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent) of 2% and a softener active ingredient concentration (total concentration of polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0138] Test Example 3 Water was mixed with water to obtain a treatment solution with a water-repellent agent 1 prepared in Reference Example 1, followed by the softener 3 prepared in Example 3. The treatment solution had a water-repellent agent active ingredient concentration (polymer concentration of the water-repellent agent) of 2% and a softener active 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 this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water-repellency test was then performed. The results are shown in Table 3.

[0139] Test Example 4 Water was mixed with water, and then softener 4 prepared in Example 4 was added to water to obtain a treatment solution with a water-repellent active ingredient concentration (polymer concentration of the water-repellent) of 4% and a softener active ingredient concentration (total concentration of polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0140] Test Example 5 Water was mixed with water to obtain a treatment solution with a water-repellent agent 2 prepared in Reference Example 2, followed by the softener 4 prepared in Example 4. The treatment solution had a water-repellent agent active ingredient concentration (polymer concentration of the water-repellent agent) of 2% and a softener active ingredient concentration (total concentration of polymer and silicone of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water-repellency test was then performed. The results are shown in Table 3.

[0141] Comparative Test Example 1 Water repellent agent 1, prepared in Reference Example 1, was added to water to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent agent) of 4%. PET cloth, cotton cloth, and nylon cloth (500 mm x 200 mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0142] Comparative Test Example 2 Water was mixed with water using the water repellent agent 1 prepared in Reference Example 1, followed by the addition of a commercially available silicone-based softener (aminosilicone emulsion; weakly cationic, 14% solids content, aminosilicone molecular weight 20000) to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent) of 4% and a softener active ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500mm x 200mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0143] Comparative Test Example 3 Water was mixed with water using the water repellent agent 1 prepared in Reference Example 1, followed by the addition of a commercially available silicone-based softener (aminosilicone emulsion; weakly cationic, 14% solids, molecular weight of aminosilicone 20000) to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent) of 2% and a softener active ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500mm x 200mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0144] Comparative Test Example 4 Water repellent agent 2, prepared in Reference Example 2, was added to water to obtain a treatment solution with a water repellent active 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 this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0145] Comparative Test Example 5 Water was mixed with water using the water repellent agent 2 prepared in Reference Example 2, followed by the addition of a commercially available silicone-based softener (aminosilicone emulsion; weakly cationic, 14% solids content, molecular weight of aminosilicone 20000) to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent) of 4% and a softener active ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500mm x 200mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0146] Comparative Test Example 6 Water was mixed with water using the water repellent agent 2 prepared in Reference Example 2, followed by the addition of a commercially available silicone-based softener (aminosilicone emulsion; weakly cationic, 14% solids, molecular weight of aminosilicone 20000) to obtain a treatment solution with a water repellent active ingredient concentration (polymer concentration of the water repellent) of 2% and a softener active ingredient concentration (silicone concentration of the softener) of 2%. PET cloth, cotton cloth, and nylon cloth (500mm x 200mm) were continuously immersed in this treatment solution, passed through a mangle, and treated with a pin tenter at 170°C for 1 minute. A water repellency test was then performed. The results are shown in Table 3.

[0147] [Table 3] [Industrial applicability]

[0148] The softening agent composition of this disclosure can be used as a softening agent to impart flexibility and water repellency to a substrate.

Claims

1. A substrate treatment agent comprising a water-repellent agent and a softening agent composition, The aforementioned softener composition is (1) Silicone polymer, (2) A water-repellent polymer selected from the group consisting of fluorine-containing polymers and non-fluorine polymers, which is polymerized in the presence of a silicone polymer. (3) A liquid medium which is water or a mixture of water and an organic solvent, (4) Emulsifier The mixture comprises the following, wherein the amount of the silicone polymer is 20% by weight or more of the total amount of the silicone polymer and the water-repellent polymer: Non-fluorinated polymers, formula: CH 2 =C(-X 21 )-C(=O)-Y 21 -(R 21 ) k (a1) [In the formula, R 21 is a hydrocarbon group having 7 to 40 carbon atoms, X21 is a hydrogen atom, a methyl group, or a halogen atom. Y21 is a group (excluding hydrocarbon groups) consisting of at least one selected from divalent to tetravalent carbon-1 hydrocarbon groups, -C6H4-, -O-, -C(=O)-, -S(=O)2-, or -NH-. k is between 1 and 3. It is a non-fluorinated polymer having repeating units derived from long-chain hydrocarbon group-containing non-fluorinated monomers, which are long-chain (meth)acrylic monomers (excluding behenyl (meth)acrylates) represented by , A substrate treatment agent wherein the amount of repeating units derived from long-chain (meth)acrylic monomers is 40 to 100% by weight relative to the water-repellent polymer.

2. The silicone polymer (1) is of formula: (R 3 -) 3 Si-O-[-Si(-R 1 ) 2 -O-] a -[-Si(-R 1 )(-X 1 -R 2 )-O-] b -Si(-R 3 ) 3 [In the formula, each of R1 is independently a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, or a C1-C4 alkoxy group.] Each of R2 is independently a functional group. Each of R3 is independently a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C1-C4 alkoxy group, or a functional group. Each of X1 is a directly bonded or divalent hydrocarbon group having 1 to 10 carbon atoms. a is a non-negative integer, b is a non-negative integer, and (a + b) is between 5 and 200. This is a polymer represented by The substrate treatment agent according to claim 1, wherein the functional group is at least one functional group selected from the group consisting of epoxy groups, amino groups, vinyl groups, (meth)acrylamide groups, (meth)acrylate groups, and hydrocarbon groups having 7 to 40 carbon atoms.

3. A fluorine-containing polymer, formula: CH 2 =C(-X 11 )-C(=O)-Y 11 -Z 11 -Rf [In the formula, X11 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, a CFX1X2 group (wherein X1 and X2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; Y 11 is -O- or -NH-; Z 11 is directly coupled, A linear or branched aliphatic group having 1 to 20 carbon atoms. Aromatic groups or cyclic aliphatic groups having 6 to 30 carbon atoms, A group represented by formula -R2(R1)N-SO2- or formula -R2(R1)N-CO- (wherein R1 is an alkyl group having 1 to 10 carbon atoms, and R2 is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms). The group represented by the formula -CH₂CH(OR₃)CH₂-(Ar-O)p- (wherein R₃ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group optionally having substituents, and p represents 0 or 1), A group represented by the formula -CH₂-Ar-(O)q- (wherein Ar is an arylene group optionally having substituents, and q is 0 or 1), or -(CH₂)m-SO₂-(CH₂)n-group or -(CH₂)m-S-(CH₂)n-group (where m is between 1 and 10, and n is between 0 and 10); Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. This is a fluorine-containing polymer having repeating units derived from a fluorine-containing monomer shown as follows: A substrate treatment agent according to claim 1 or 2.

4. The substrate treatment agent according to claim 3, wherein in the fluorine-containing monomer, X 11 is a hydrogen atom, a methyl group, or a chlorine atom, and the number of carbon atoms of Rf is 1 to 6.

5. In the long chain (meth)acrylic monomer, Y 21 is -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C 6 H 4 -, -O-(CH 2 ) m -O-, -NH-(CH 2 ) m -NH-, -O-(CH 2 ) m -NH-, -NH-(CH 2 ) m -O-, -O-(CH 2 ) m -O-C(=O)-, -O-(CH 2 ) m -C(=O)-O-, -NH-(CH 2 ) m -OC(=O)-, -NH-(CH 2 ) m -C(=O)-O-, -O-(CH 2 ) m -OC(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-O-, -O-(CH 2 ) m -C(=O)-NH-, -O-(CH 2 ) m -NH-C(=O)-, -O-(CH 2 ) m -NH-C(=O)-NH-, -O-(CH 2 ) m -O-C 6 H 4 -, -O-(CH 2 ) m -NH-S(=O) 2 -, -O-(CH 2 ) m -S(=O) 2 -NH-, -NH-(CH 2 ) m -O-C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-O-, -NH-(CH 2 ) m -C(=O)-NH-, -NH-(CH 2 ) m -NH-C(=O)-, -NH-(CH 2 ) m -NH-C(=O)-NH-, -NH-(CH 2 ) m -O-C 6 H 4 -, -NH-(CH 2 ) m -NH-C 6 H 4 -, -NH-(CH 2 ) m -NH-S(=O) 2 -, or -NH-(CH 2 ) m -S(=O) 2 -NH- [In the formula, m is between 1 and 5.] The substrate treatment agent according to claim 3.

6. The amount of silicone polymer (1) is 30 to 90% by weight relative to the total weight of silicone polymer (1) and water-repellent polymer (2), The amount of the liquid medium (3) is 5 to 99.9% by weight relative to the softener composition. The substrate treatment agent according to any one of claims 1 to 5, wherein the amount of emulsifier (4) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of silicone polymer (1) and water-repellent polymer (2).

7. The substrate treatment agent according to claim 1 or 2, wherein the water-repellent polymer (2) further comprises repeating units formed from a non-fluorine, non-crosslinkable monomer and / or a non-fluorine, crosslinkable monomer.

8. A non-fluorine, non-crosslinkable monomer is In fluorine-containing polymers, formula: CH 2 =CA 21 -C(=O)-Y 21 -A 22 [In the formula, A21 is a hydrogen atom or a methyl group, A22 is a straight-chain or branched aliphatic hydrocarbon group having 7 to 40 carbon atoms. Y21 is either -O- or -NH-. It is a long-chain (meth)acrylic monomer represented by, or In fluorine-containing polymers or non-fluorine polymers, the formula is: CH 2 =CA 31 -C(=O)-Y 31 -A 32 [In the formula, A31 is a hydrogen atom or a methyl group, A32 is a cyclic hydrocarbon group having 4 to 20 carbon atoms. Y 31 is either -O- or -NH-. The substrate treatment agent according to claim 7, which is a cyclic hydrocarbon group-containing (meth)acrylic monomer represented by .

9. The substrate treatment agent according to claim 7, wherein the nonfluorine 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, the reactive group being at least one 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.

10. In a water-repellent polymer (2), The total amount of fluorine-containing monomers and long-chain hydrocarbon group-containing non-fluorine monomers is 32 to 98% by weight relative to the water-repellent polymer. The amount of non-fluorine, non-crosslinked monomer is 2 to 68% by weight relative to the water-repellent polymer. The substrate treatment agent according to any one of claims 7 to 9, wherein the amount of non-fluorine crosslinkable monomer is 0.1 to 20 parts by weight per 100 parts by weight of the total of fluorine-containing monomer and long-chain hydrocarbon group-containing non-fluorine monomer.

11. A method for producing a substrate treatment agent according to any one of claims 1 to 10, comprising polymerizing monomers constituting the water-repellent polymer (2) in the presence of a silicone polymer (1) to produce a water-repellent polymer (2) and obtain a softener composition.

12. A method for treating a substrate with a substrate treatment agent according to any one of claims 1 to 10.

13. A substrate treated with the substrate treatment agent according to any one of claims 1 to 10.