Fluorine-free water repellent composition and method for producing water-repellent textile products

Abstract

To provide a water repellent aid that can improve the water repellent durability of a non-fluorine water repellent.SOLUTION: A water repellent aid for non-fluorine water repellent includes an organo-modified silicone represented by general formula (1). [In formula (1), R20, R21 and R22 each independently represent a hydrogen atom, methyl group, ethyl group, or C1-4 alkoxy group, R23 represents either a C8-40 hydrocarbon group having an aromatic ring or a C3-22 alkyl group, R30, R31, R32, R33, R34 and R35 each independently represent a hydrogen atom, methyl group, ethyl group, C1-4 alkoxy group, C8-40 hydrocarbon group having an aromatic ring, or C3-22 alkyl group, a represents an integer of 0 or higher, b represents an integer of 1 or higher, and (a+b) is 10 to 200].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water repellent auxiliary, a non-fluorine-based water repellent composition, and a method for producing a water repellent textile product. [Background technology]

[0002] Fluorine-based water repellents having a fluorine-containing group have been known, and textile products, etc., whose surfaces are imparted with water repellency by treating the textile products with such fluorine-based water repellents are known. Such fluorine-based water repellents are generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group.

[0003] Although textile products treated with fluorine-based water repellents exhibit excellent water repellency, the orientation of the fluoroalkyl groups must be adjusted to achieve this, and therefore, after the fluorine-based water repellent agent has been applied to the textile product, it must be heat-treated at temperatures exceeding 130°C. However, heat treatment at high temperatures requires a large amount of energy, which is problematic given the international trend toward energy conservation.

[0004] Furthermore, since the monomer having a fluoroalkyl group is expensive, it is not satisfactory from an economical point of view, and furthermore, since the monomer having a fluoroalkyl group is difficult to decompose, it is problematic from an environmental point of view.

[0005] On the other hand, in the field of water-repellent finishing of textile products, there is a demand for water-repellent agents that can impart excellent water repellency to textile products even at low concentrations and low heat treatment temperatures in order to stabilize quality and reduce costs.

[0006] Therefore, in recent years, research has been conducted on non-fluorine-based water repellents that do not contain fluorine. For example, Non-Patent Document 1 discloses a water repellent in which a hydrocarbon compound such as paraffin or wax, a fatty acid metal salt, or an alkyl urea is emulsified and dispersed.

[0007] Furthermore, Patent Document 1 proposes a water repellent agent in which a specific non-fluorinated polymer is emulsified and dispersed, with the aim of imparting water repellency comparable to that of conventional fluorinated water repellents. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] "Super Water-Repellent Processing, a Complete Overview of Processing Agents and New Trends in Breathable Waterproof Materials," published by Osaka Chemical Marketing Center Co., Ltd., 1996, pp. 7-9 [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-328624 Summary of the Invention [Problem to be solved by the invention]

[0010] However, conventional water repellents sometimes fail to provide sufficient durable water repellency.

[0011] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a water repellent auxiliary capable of improving the durable water repellency of a non-fluorinated water repellent, a non-fluorinated water repellent composition using the same, and a method for producing a water-repellent textile product. [Means for solving the problem]

[0012] The present invention provides a water repellent aid for use with non-fluorine-based water repellents, which water repellent aid contains an organo-modified silicone represented by the following general formula (1).

[0013] [ka] [In formula (1), R 20 , R 21 and R 22each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23 represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, multiple R 20 and R 21 may be the same or different, and when b is 2 or more, there are multiple R 22 and R 23 may be the same or different.

[0014] The water repellent auxiliary of the present invention, when used in combination with a non-fluorine-based water repellent, can improve the durable water repellency of the non-fluorine-based water repellent.

[0015] The present invention also provides a non-fluorine-based water repellent composition comprising the water repellent auxiliary according to the present invention and a non-fluorine-based water repellent.

[0016] The non-fluorine-based water repellent may contain a non-fluorine-based polymer containing a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1).

[0017] [ka] [In formula (A-1), R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.

[0018] The non-fluorinated polymer may further contain a structural unit derived from at least one reactive emulsifier (B) selected from the group consisting of (B1) a compound represented by the following general formula (I-1) having an HLB value of 7 to 18, (B2) a compound represented by the following general formula (II-1) having an HLB value of 7 to 18, and (B3) a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, the compound having an HLB value of 7 to 18.

[0019] [ka] [In formula (I-1), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0020] [ka] [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0021] The above-mentioned non-fluorine-based polymer may further contain a structural unit derived from at least one monomer (E) of vinyl chloride and vinylidene chloride.

[0022] The non-fluorine-based water repellent may contain a non-fluorine-based polymer obtained by emulsion polymerization or dispersion polymerization of an emulsion or dispersion containing the (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) above.

[0023] The emulsion or dispersion may further contain at least one reactive emulsifier (B) selected from (B1) a compound represented by general formula (I-1) above and having an HLB of 7 to 18, (B2) a compound represented by general formula (II-1) above and having an HLB of 7 to 18, and (B3) a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group and having an HLB of 7 to 18.

[0024] The emulsion or dispersion may further contain at least one monomer (E) of vinyl chloride and vinylidene chloride.

[0025] In the non-fluorine-based water repellent composition according to the present invention, the content of the organo-modified silicone may be 1 to 50 parts by mass relative to 100 parts by mass of the non-fluorine-based polymer.

[0026] The present invention also provides a method for producing a water-repellent textile product, which comprises a step of treating a textile product with a treatment liquid containing the above-described non-fluorinated water repellent composition according to the present invention.

[0027] According to the method for producing water-repellent textile products of the present invention, by using a non-fluorinated water repellent composition containing the water repellent auxiliary of the present invention, water-repellent textile products having excellent durable water repellency can be stably produced. Furthermore, the method for producing water-repellent textile products of the present invention does not require high-temperature heat treatment, thereby saving energy, and the use of a non-fluorinated water repellent can reduce the burden on the environment. [Effects of the Invention]

[0028] According to the present invention, it is possible to provide a water repellent auxiliary capable of improving the durable water repellency of a non-fluorinated water repellent, and a non-fluorinated water repellent composition containing the same.

[0029] Furthermore, the non-fluorine-based water repellent composition of the present invention exhibits excellent water repellency despite being a water repellent composition that does not contain a fluoroalkyl group or a compound containing fluorine, and can be used as a substitute for fluorine-based water repellents, thereby eliminating concerns about the impact on fluorine supply sources and the environment, etc. While it is usually preferable to perform a heat treatment after the water repellent composition has been applied to a textile product or the like, the non-fluorine-based water repellent composition of the present invention does not use a monomer having a fluoroalkyl group, and therefore can exhibit high water repellency even when heat-treated under mild conditions of 130°C or less. Furthermore, when heat-treated at a high temperature exceeding 130°C, the heat treatment time can be shorter than in the case of fluorine-based water repellents. Therefore, heat-induced deterioration of the treated object is suppressed, resulting in a softer texture, and the amount of heat required for heat treatment can be reduced, making it cost-effective.

[0030] Furthermore, according to the present invention, by using a specific reactive emulsifier instead of a general surfactant as an emulsifying dispersant used in the emulsion or dispersion polymerization of a non-fluorinated polymer, the amount of surfactant contained in the water repellent composition can be reduced, which results in suppressing the decrease in water repellency of the resulting textile product and the like, and achieving higher water repellency than that of conventional non-fluorinated water repellents. DETAILED DESCRIPTION OF THE INVENTION

[0031] The water repellent aid for a non-fluorinated water repellent of this embodiment contains an organo-modified silicone represented by the following general formula (1): In the following general formula (1), the structural units may be arranged in blocks, randomly, or alternately.

[0032] [ka] [In formula (1), R 20 , R 21 and R 22 each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms; R 23represents a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a represents an integer of 0 or more; b represents an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, multiple R 20 and R 21 may be the same or different, and when b is 2 or more, there are multiple R 22 and R 23 may be the same or different.

[0033] In the organo-modified silicone of this embodiment, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. R 20 , R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0034] Examples of the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms and a group represented by the following general formula (2) or (3).

[0035] [ka] [In formula (2), R 40 represents an alkylene group having 2 to 6 carbon atoms, and R 41 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and c represents an integer of 0 to 3. When c is 2 or 3, multiple R 41may be the same or different.]

[0036] The alkylene group may be linear or branched.

[0037] [ka] [In formula (3), R 42 represents an alkylene group having 2 to 6 carbon atoms, and R 43 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and d represents an integer of 0 to 3. When d is 2 or 3, multiple R 43 may be the same or different.]

[0038] The alkylene group may be linear or branched.

[0039] Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

[0040] In the group represented by the general formula (2), R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0041] In the group represented by the general formula (3), R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0042] As the hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, the aralkyl group having 8 to 40 carbon atoms and the group represented by the general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the aralkyl group having 8 to 40 carbon atoms is more preferred in that it can improve the water repellency of the resulting textile product.

[0043] The alkyl group having 3 to 22 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 22 carbon atoms include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a myristyl group, a cetyl group, and a stearyl group. As the alkyl group having 3 to 22 carbon atoms, an alkyl group having 8 to 20 carbon atoms is preferred, and an alkyl group having 12 to 18 carbon atoms is more preferred, in terms of improving the water repellency of the resulting textile product.

[0044] In the organo-modified silicone of this embodiment, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0045] In the organo-modified silicone of this embodiment, a is an integer of equal to or greater than 0. From the viewpoints of ease of industrial production, ease of availability, and superior peel strength of the resulting textile product against resin coatings, a is preferably equal to or less than 40, and more preferably equal to or less than 30.

[0046] In the organo-modified silicone of this embodiment, (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.

[0047] The organo-modified silicone of this embodiment can be synthesized by a conventionally known method, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an aromatic compound and / or an α-olefin having a vinyl group.

[0048] Examples of the silicone having a SiH group include methylhydrogensilicone and a copolymer of dimethylsiloxane and methylhydrogensiloxane, each having a degree of polymerization of 10 to 200. Among these, methylhydrogensilicone is preferred because it is easy to produce industrially and is readily available.

[0049] The aromatic compound having a vinyl group is represented by the formula (1) R 23 In the above formula, the aromatic compound is a compound from which a hydrocarbon group having an aromatic ring and 8 to 40 carbon atoms is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0050] The above α-olefin is represented by R in the above general formula (1). 23In the above formula, it is a compound from which an alkyl group having 3 to 22 carbon atoms is derived. Examples of α-olefins include α-olefins having 3 to 22 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

[0051] The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise or all at once, if necessary, in the presence of a catalyst.

[0052] The amounts of the SiH group-containing silicone, vinyl group-containing aromatic compound, and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone, etc.

[0053] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0054] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. 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.

[0055] The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0056] The non-fluorine-based water repellent composition of this embodiment will be described.

[0057] The non-fluorine-based water repellent composition of this embodiment contains the water repellent auxiliary of this embodiment and a non-fluorine-based water repellent.

[0058] The non-fluorine-based water repellent preferably contains a non-fluorine-based polymer containing a structural unit derived from a (meth)acrylic acid ester monomer (A) (hereinafter also referred to as "component (A)") represented by the following general formula (A-1), in that it has excellent storage stability, can impart sufficient water repellency to textile products and the like even without heat treatment, and can provide water-repellent textile products with excellent feel and water repellency.

[0059] [ka] [In formula (A-1), R 1 represents hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.

[0060] Here, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester", and has the same meaning as "(meth)acrylic acid", "(meth)acrylamide", etc.

[0061] The (meth)acrylic acid ester monomer (A) used in this embodiment and represented by the general formula (A-1) has a monovalent hydrocarbon group having 12 or more carbon atoms, which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring. Among these, linear groups are preferred, and linear alkyl groups are more preferred. In this case, the water repellency is improved. When the monovalent hydrocarbon group having 12 or more carbon atoms has a substituent, the substituent may be one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In this embodiment, in the general formula (A-1), R 2 is preferably an unsubstituted hydrocarbon group.

[0062] The number of carbon atoms in the hydrocarbon group is preferably 12 to 24. If the number of carbon atoms is less than 12, the non-fluorinated polymer cannot exhibit sufficient water repellency when adhered to a textile product, etc. On the other hand, if the number of carbon atoms is more than 24, the texture of the textile product tends to be rough and hard when adhered to the textile product, etc., compared to when the number of carbon atoms is within the above range.

[0063] The number of carbon atoms in the hydrocarbon group is more preferably 12 to 21. When the number of carbon atoms is within this range, the water repellency and feel are particularly excellent. A particularly preferred hydrocarbon group is a linear alkyl group having 12 to 18 carbon atoms.

[0064] Examples of the component (A) include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, ceryl (meth)acrylate, and melissyl (meth)acrylate.

[0065] The (A) component may have at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent. In this case, the durable water repellency of the resulting textile product can be further improved. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. Furthermore, when the (A) component has an amino group, the feel of the resulting textile product can be further improved.

[0066] The component (A) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0067] The component (A) may be used alone or in combination of two or more.

[0068] From the viewpoint of durable water repellency of the resulting textile product, it is preferable to use a combination of an acrylic acid ester monomer (a1) and a methacrylic acid ester monomer (a2) as the component (A). The ratio (a1) / (a2) of the mass of the blended component (a1) to the mass of the blended component (a2) is preferably 30 / 70 to 90 / 10, more preferably 40 / 60 to 85 / 15, and even more preferably 50 / 50 to 80 / 20. When (a1) / (a2) is within the above range, the durable water repellency of the resulting textile product is improved. When (a1) / (a2) is more than 90 / 10 or less than 30 / 70, the durable water repellency of the resulting textile product tends to decrease.

[0069] The total constituent ratio of the monomers of the component (A) in the non-fluorine-based polymer is preferably 50 to 100 mass%, more preferably 55 to 97 mass%, and even more preferably 60 to 95 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoint of the water repellency and durable water repellency of the resulting textile product.

[0070] The weight-average molecular weight of the non-fluorine-based polymer is preferably 100,000 or more. If the weight-average molecular weight is less than 100,000, the water repellency of the resulting textile product tends to be insufficient. Furthermore, the weight-average molecular weight of the non-fluorine-based polymer is more preferably 500,000 or more. In this case, the resulting textile product can exhibit more sufficient water repellency. The upper limit of the weight-average molecular weight of the non-fluorine-based polymer is preferably about 5,000,000.

[0071] In this embodiment, the melt viscosity of the non-fluorinated polymer at 105°C is preferably 1000 Pa·s or less. If the melt viscosity at 105°C exceeds 1000 Pa·s, the feel of the obtained textile product tends to be rough and hard. Furthermore, if the melt viscosity of the non-fluorinated polymer is too high, when the non-fluorinated polymer is emulsified or dispersed to form a water repellent composition, the non-fluorinated polymer may precipitate or settle, and the storage stability of the water repellent composition tends to decrease. It is more preferable that the melt viscosity at 105°C is 500 Pa·s or less. In this case, the obtained textile product etc. will have sufficient water repellency and an excellent feel.

[0072] "Melt viscosity at 105°C" is determined by placing 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester (e.g., Shimadzu CFT-500), holding the temperature at 105°C for 6 minutes, and measuring the melt viscosity at 100 kgf / cm using a plunger. 2 This refers to the viscosity when measured under a load of 1000 kJ / cm.

[0073] When the weight-average molecular weights of non-fluorine-based polymers are the same, the higher the blend ratio of the non-fluorine-based (meth)acrylic acid ester monomer, the higher the water repellency of the textile product to which the polymer is attached tends to be. Furthermore, copolymerization of a copolymerizable non-fluorine-based monomer can improve the performance of the textile product to which the polymer is attached, such as durable water repellency and feel.

[0074] In addition to component (A), the non-fluorinated polymer preferably contains, as a monomer component, at least one reactive emulsifier (B) (hereinafter also referred to as "component (B)") selected from the group consisting of: (B1) a compound represented by general formula (I-1) below and having an HLB value of 7 to 18; (B2) a compound represented by general formula (II-1) below and having an HLB value of 7 to 18; and (B3) a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, the compound having an HLB value of 7 to 18.

[0075] [ka] [In formula (I-1), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0076] [ka] [In formula (II-1), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and Y 2 represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0077] The term "reactive emulsifier" refers to an emulsifying dispersant having radical reactivity, i.e., a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.

[0078] "HLB" refers to the HLB value calculated by the Griffin method, assuming that the ethyleneoxy group is a hydrophilic group and all other groups are lipophilic groups.

[0079] The HLB of the compounds (B1) to (B3) used in this embodiment is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorinated polymer (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of storage stability of the non-fluorinated water repellent, it is more preferable to use in combination two or more reactive emulsifiers (B) having different HLBs within the above range.

[0080] In the reactive emulsifier (B1) represented by the general formula (I-1) used in this embodiment, R 3 is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated polymer of this embodiment. Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 1 The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure.

[0081] As the compound represented by the above general formula (I-1), a compound represented by the following general formula (I-2) is preferred.

[0082] [ka] [In formula (I-2), R 3 represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and m can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 80 is preferred. When m is 2 or more, m A 1 O may be the same or different.]

[0083] In the compound represented by the above general formula (I-2), R 3 is hydrogen or a methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of the non-fluorinated polymer. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The types and combinations of O and the number m can be appropriately selected so as to fall within the above HLB range. In terms of emulsion stability of the non-fluorinated polymer, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A 1 O may be the same or different. 1 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0084] The reactive emulsifier (B1) represented by the general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0085] In the reactive emulsifier (B2) represented by the general formula (II-1) used in this embodiment, R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, and examples thereof include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of emulsion stability of non-fluorinated polymers, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0086] Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2The type, combination, and number of alkyleneoxy groups in the formula (I) can be appropriately selected so as to fall within the above-mentioned HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure. In terms of emulsion stability of the non-fluorinated polymer, the alkyleneoxy group is preferably an ethyleneoxy group.

[0087] The compound represented by the above general formula (II-1) is preferably a compound represented by the following general formula (II-2).

[0088] [ka] [In formula (II-2), R 4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A 2 O may be the same or different.]

[0089] R in the compound represented by the above general formula (II-2) 4 represents R in the above general formula (II-1). 4 The same can be mentioned.

[0090] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of non-fluorinated polymers, A 2 The types and combinations of O and the number of n can be appropriately selected so as to fall within the above HLB range. 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and further preferably an integer of 8 to 14. When n is 2 or more, n A 2 O may be the same or different. 2When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0091] The reactive emulsifier (B2) represented by the general formula (II-2) used in this embodiment can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group using a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

[0092] Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells and are collectively known as cardanol.

[0093] The reactive emulsifier (B3) used in this embodiment is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a fat or oil having a hydroxyl group and a polymerizable unsaturated group, and the fat or oil has an HLB value of 7 to 18. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoleidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of the non-fluorinated polymer, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above-mentioned HLB range, and from the viewpoint of emulsion stability of the non-fluorinated polymer, 20 to 50 moles are more preferred, and 25 to 45 moles are even more preferred. Furthermore, when two or more types of alkylene oxides are used, they may have a block addition structure or a random addition structure.

[0094] The reactive emulsifier (B3) used in this embodiment can be synthesized by adding an alkylene oxide to a fat or oil having a hydroxyl group and a polymerizable unsaturated group using a conventionally known method, and is not particularly limited. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C.

[0095] The proportion of the monomer of component (B) in the non-fluorine-based polymer is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and even more preferably 3 to 10 mass%, relative to the total amount of monomer components constituting the non-fluorine-based polymer, from the viewpoint of improving the water repellency of the obtained textile product and the emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the non-fluorine-based polymer.

[0096] The non-fluorine-based polymer contained in the non-fluorine-based water repellent preferably contains, in addition to component (A), at least one second (meth)acrylic acid ester monomer (C) (hereinafter also referred to as "component C") selected from the group consisting of the following (C1), (C2), (C3), (C4) and (C5) as a monomer component, in order to improve the durable water repellency of the resulting textile product.

[0097] (C1) (Meth)acrylic acid ester monomers other than (C5) and represented by the following general formula (C-1): [ka] [In formula (C-1), R 5 represents hydrogen or a methyl group, and R 6 represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.]

[0098] (C2) A (meth)acrylic acid ester monomer represented by the following general formula (C-2): [ka] [In formula (C-2), R 7 represents hydrogen or a methyl group, and R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

[0099] (C3) A methacrylic acid ester monomer represented by the following general formula (C-3): [ka] [In formula (C-3), R 9 represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.]

[0100] (C4) A (meth)acrylic acid ester monomer represented by the following general formula (C-4): [ka] [In formula (C-4), R 10 represents hydrogen or a methyl group, p represents an integer of 2 or greater, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.]

[0101] (C5) A (meth)acrylic acid ester monomer represented by the following general formula (C-5): [ka] [In formula (C-5), R 11 represents hydrogen or a methyl group, and R 12 represents a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having a hydroxyl group and at least one functional group selected from the group consisting of a chloro group and a bromo group.]

[0102] The monomer (C1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety, and is a (meth)acrylic acid ester monomer other than the monomer (C5). From the viewpoint of being reactive with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a non-fluorine-containing polymer containing the monomer (C1) having a group reactive with these crosslinking agents is applied to a textile product together with the crosslinking agent, the durable water repellency of the resulting textile product can be improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0103] The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, a linear and / or saturated hydrocarbon group is preferred in terms of improving the durable water repellency of the resulting textile product.

[0104] Specific examples of the monomer (C1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving the feel of the resulting textile product.

[0105] The proportion of the monomer (C1) in the non-fluorine-based polymer is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoints of water repellency and feel of the resulting textile product.

[0106] The monomer (C2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. From the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and if alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred, in that they can improve the durable water repellency of the resulting textile product.

[0107] The proportion of the monomer (C2) in the non-fluorine-based polymer is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoints of water repellency and feel of the resulting textile product.

[0108] The monomer (C3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms or a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the chain hydrocarbon group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred, in that they can improve the durable water repellency of the resulting textile product.

[0109] The proportion of the monomer (C3) in the non-fluorine-based polymer is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoints of water repellency and feel of the resulting textile product.

[0110] The monomer (C4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, polyfunctional (meth)acrylic acid ester monomers having three or more (meth)acryloyloxy groups in one molecule, in which T in the general formula (C-4) is a (meth)acryloyloxy group, are preferred. In formula (C-4), the p Ts may be the same or different. Specific examples of the compound include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of improving the durable water repellency of the resulting textile product.

[0111] The proportion of the monomer (C4) in the non-fluorine-based polymer is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoints of water repellency and feel of the resulting textile product.

[0112] The monomer (C5) has a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. 11 is hydrogen or a methyl group. In terms of the durable water repellency of the resulting textile product, R 11 is preferably a methyl group.

[0113] R 12is a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having at least one functional group selected from the group consisting of a chloro group and a bromo group and a hydroxyl group. The chain saturated hydrocarbon group may be linear or branched. When the chain saturated hydrocarbon group is linear, the durable water repellency of the resulting textile product is more excellent. The number of carbon atoms in the chain saturated hydrocarbon group is preferably 3 to 4, and more preferably 3, from the viewpoint of durable water repellency of the resulting textile product.

[0114] From the viewpoint of durable water repellency of the resulting textile product, the above-mentioned chain saturated hydrocarbon group preferably has one or two chloro groups and one hydroxyl group, and more preferably has one chloro group and one hydroxyl group. Also, from the viewpoint of durable water repellency of the resulting textile product, the chain saturated hydrocarbon group has a β-position (CH2=CR 11 It is more preferable that the chain saturated hydrocarbon group has a hydroxyl group on the carbon atom adjacent to the carbon atom bonded to (CO)O-. Specific examples of the chain saturated hydrocarbon group include a 3-chloro-2-hydroxypropyl group, a 3-chloro-2-hydroxybutyl group, a 5-chloro-2-hydroxypentyl group, a 3-chloro-2-hydroxy-2-methylpropyl group, and a 3-bromo-2-hydroxypropyl group.

[0115] Specific examples of the monomer (C5) include 3-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxybutyl (meth)acrylate, 5-chloro-2-hydroxypentyl (meth)acrylate, and 3-bromo-2-hydroxypropyl (meth)acrylate. Among these, 3-chloro-2-hydroxypropyl (meth)acrylate is preferred, and 3-chloro-2-hydroxypropyl methacrylate is more preferred, in terms of improving the durable water repellency of the resulting textile product.

[0116] The proportion of the monomer (C5) in the non-fluorine-based polymer is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoint of durable water repellency of the resulting textile product.

[0117] The total constituent ratio of the monomers of the component (C) in the non-fluorine-based polymer is preferably 1 to 30 mass%, more preferably 3 to 25 mass%, and even more preferably 5 to 20 mass%, based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoints of water repellency and feel of the resulting textile product.

[0118] The non-fluorine-based polymer contained in the non-fluorine-based water repellent may contain, in addition to the components (A), (B), and (C), a monofunctional monomer (D) (hereinafter also referred to as "component (D)") copolymerizable with these components, within a range that does not impair the effects of the present invention.

[0119] Examples of the monomer (D) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than components (A) and (C), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other fluorine-free vinyl monomers other than component (E). Note that the (meth)acrylic acid esters having a hydrocarbon group other than components (A) and (C) may have a substituent on the hydrocarbon group such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group, or may have a substituent other than a group reactive with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, ester bond, amide bond, urethane bond, or the like. Examples of (meth)acrylic acid esters other than components (A) and (C) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Among these, (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting textile product against coating.

[0120] The proportion of the monomer of component (D) in the non-fluorine-based polymer is preferably 10 mass % or less based on the total amount of the monomer components constituting the non-fluorine-based polymer, from the viewpoint of the water repellency and feel of the resulting textile product.

[0121] The non-fluorine-based polymer contained in the non-fluorine-based water repellent preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, as this improves the durable water repellency of the resulting textile product. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. Furthermore, the non-fluorine-based polymer preferably has an amino group, as this also improves the feel of the resulting textile product.

[0122] The non-fluorinated polymer contained in the non-fluorinated water repellent preferably contains, in addition to component (A), at least one monomer (E) of vinyl chloride and vinylidene chloride (hereinafter also referred to as "component (E)") as a monomer component, in that this can improve the water repellency and peel strength against coating of the resulting textile product.

[0123] The at least one monomer (E) of vinyl chloride and vinylidene chloride used in this embodiment is preferably vinyl chloride in terms of the water repellency of the resulting textile product and the peel strength against coating.

[0124] The proportion of the monomer of component (E) in the non-fluorine-based polymer is preferably 1 to 45 mass%, more preferably 3 to 40 mass%, and even more preferably 5 to 35 mass%, based on the total amount of monomer components constituting the non-fluorine-based polymer, from the viewpoint of improving the peel strength of the resulting textile product against coating.

[0125] Additives may be added to the water repellent composition of the present embodiment as needed. Examples of additives include other water repellents, crosslinking agents, antibacterial and deodorizing agents, flame retardants, antistatic agents, softeners, and wrinkle inhibitors.

[0126] Next, a method for producing a non-fluorine-based water repellent agent containing a non-fluorine-based polymer will be described.

[0127] The non-fluorine-containing water repellent containing a non-fluorine-containing polymer can be produced by radical polymerization. Among these radical polymerization methods, emulsion polymerization or dispersion polymerization is preferred from the viewpoints of the performance of the resulting water repellent and the environment.

[0128] For example, a non-fluorinated polymer can be obtained by emulsion polymerization or dispersion polymerization of a (meth)acrylic acid ester monomer (A) represented by the above general formula (A-1) in a medium. More specifically, for example, component (A) and, if necessary, components (B), (C), (D), and (E), as well as an emulsifying aid or dispersing aid, are added to a medium, and the resulting mixture is emulsified or dispersed to obtain an emulsion or dispersion. A polymerization initiator is added to the resulting emulsion or dispersion to initiate the polymerization reaction, polymerizing the monomer and reactive emulsifier. Examples of means for emulsifying or dispersing the above-mentioned mixture include a homomixer, a high-pressure emulsifier, and ultrasound.

[0129] The emulsifying aid or dispersing aid (hereinafter also referred to as "emulsifying aid") can be one or more selected from nonionic surfactants other than the reactive emulsifier (B), cationic surfactants, anionic surfactants, and amphoteric surfactants. The content of the emulsifying aid is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total monomers. If the content of the emulsifying aid is less than 0.5 parts by mass, the dispersion stability of the mixed liquid tends to decrease compared to when the content of the emulsifying aid is within the above range. If the content of the emulsifying aid is more than 30 parts by mass, the water repellency of the resulting non-fluorinated polymer tends to decrease compared to when the content of the emulsifying aid is within the above range.

[0130] The medium for emulsion polymerization or dispersion polymerization is preferably water, and water may be mixed with an organic solvent as needed. The organic solvent is not particularly limited as long as it is miscible with water, and examples thereof include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, and glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol. The ratio of water to the organic solvent is not particularly limited.

[0131] As the polymerization initiator, known polymerization initiators such as azo-based, peroxide-based, or redox-based initiators can be used as appropriate. The content of the polymerization initiator is preferably 0.01 to 2 parts by mass per 100 parts by mass of all monomers. When the content of the polymerization initiator is within the above range, a non-fluorine-based polymer having a weight-average molecular weight of 100,000 or more can be efficiently produced.

[0132] In addition, in the polymerization reaction, a chain transfer agent such as dodecyl mercaptan or t-butyl alcohol may be used for the purpose of adjusting the molecular weight. The content of the chain transfer agent is preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less, relative to 100 parts by mass of all monomers. If the content of the chain transfer agent exceeds 0.3 parts by mass, the molecular weight decreases, and it tends to become difficult to efficiently produce a non-fluorinated polymer having a weight average molecular weight of 100,000 or more.

[0133] A polymerization inhibitor may be used to adjust the molecular weight, and the addition of a polymerization inhibitor makes it possible to easily obtain a non-fluorine-containing polymer having a desired weight average molecular weight.

[0134] The temperature of the polymerization reaction is preferably 20° C. to 150° C. If the temperature is below 20° C., the polymerization tends to be insufficient compared to when the temperature is within the above range, and if the temperature exceeds 150° C., it may be difficult to control the reaction heat.

[0135] In the polymerization reaction, the weight average molecular weight of the resulting non-fluorinated polymer can be adjusted by increasing or decreasing the contents of the above-mentioned polymerization initiator, chain transfer agent, and polymerization inhibitor, and the melt viscosity at 105°C can be adjusted by increasing or decreasing the content of the polyfunctional monomer and the content of the polymerization initiator. Note that, when it is desired to decrease the melt viscosity at 105°C, the content of the monomer having two or more polymerizable functional groups can be decreased or the content of the polymerization initiator can be increased.

[0136] The content of the non-fluorinated polymer in the polymer emulsion or dispersion obtained by emulsion polymerization or dispersion polymerization is preferably 10 to 50 mass %, more preferably 20 to 40 mass %, based on the total amount of the emulsion or dispersion, from the viewpoints of storage stability and handleability of the composition.

[0137] The non-fluorine-based water repellent composition of this embodiment can be produced by mixing the water repellent auxiliary of this embodiment and the non-fluorine-based water repellent.

[0138] The amount of the organo-modified silicone represented by the general formula (1) in the non-fluorine-based water repellent composition of this embodiment is preferably 1 to 10 mass %, and more preferably 3 to 7 mass %, from the viewpoint of durable water repellency of the resulting textile product.

[0139] Furthermore, in terms of durable water repellency of the resulting textile product, the blending amount of the organo-modified silicone represented by the above general formula (1) in the non-fluorinated water repellent composition of this embodiment is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 10 to 25 parts by mass, per 100 parts by mass of the non-fluorinated polymer.

[0140] A method for producing the water-repellent textile product of this embodiment will be described.

[0141] The water-repellent textile product of this embodiment can be obtained by treating a textile product with a treatment liquid containing the above-mentioned non-fluorinated water repellent composition. The material for such textile products is not particularly limited, and examples thereof include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The textile product may be in any form, such as fiber, yarn, cloth, woven fabric, knitted fabric, cloth in the form of clothing, carpet, nonwoven fabric, or paper.

[0142] Examples of methods for treating textile products with the treatment liquid include processing methods such as immersion, spraying, and coating, and processing methods using a cleaning method, etc. When the non-fluorinated water repellent composition contains water, it is preferable to dry the composition after it has been applied to the textile product in order to remove the water.

[0143] Furthermore, after treating a textile product with the non-fluorine-based water repellent composition of this embodiment, it is preferable to appropriately heat treat the textile product. While there are no particular limitations on the temperature conditions, the use of the non-fluorine-based water repellent composition of this embodiment allows the textile product to exhibit sufficiently good water repellency under mild conditions of 100 to 130°C. The temperature conditions may be high-temperature treatment at 130°C or higher (preferably up to 200°C), and in such cases, it is possible to shorten the treatment time compared to conventional treatments using fluorine-based water repellents. Therefore, with the water-repellent textile product of this embodiment, deterioration of the textile product due to heat is suppressed, the texture of the textile product becomes soft during the water-repellent treatment, and sufficient water repellency can be imparted to the textile product under mild heat treatment conditions, i.e., low-temperature curing conditions.

[0144] In particular, when it is desired to improve durable water repellency, it is preferable to water-repellent a textile product by a method including the above-mentioned step of treating the textile product with a treatment liquid containing a non-fluorinated water repellent composition, and the step of attaching a crosslinking agent, typically methylol melamine or a compound having one or more isocyanate groups or blocked isocyanate groups, to the textile product and heating it. Furthermore, when it is desired to further improve durable water repellency, it is preferable that the non-fluorinated water repellent composition contains a non-fluorinated polymer obtained by copolymerizing a monomer having a functional group reactive with the above-mentioned crosslinking agent.

[0145] Examples of compounds having one or more isocyanate groups include monoisocyanates such as butyl isocyanate, phenyl isocyanate, tolyl isocyanate, and naphthalene isocyanate; diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; and trimers and trimethylolpropane adducts of these isocyanurate rings. Examples of compounds having one or more blocked isocyanate groups include compounds in which the isocyanate groups of the above-mentioned compounds having isocyanate groups are protected with a blocking agent. Examples of blocking agents used in this case include organic blocking agents such as secondary or tertiary alcohols, active methylene compounds, phenols, oximes, and lactams, as well as bisulfites such as sodium bisulfite and potassium bisulfite. The above-mentioned crosslinking agents may be used alone or in combination.

[0146] The crosslinking agent can be attached to the object to be treated (textile product) by, for example, immersing the object to be treated in a treatment liquid prepared by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing the crosslinking agent in water, and then drying the treatment liquid attached to the object to be treated. The crosslinking agent attached to the object to be treated is then heated to promote a reaction between the crosslinking agent and the object to be treated and the non-fluorinated polymer. To promote the crosslinking agent reaction sufficiently and more effectively improve washing durability, the heating is preferably performed at 110 to 180°C for 1 to 5 minutes. The step of attaching the crosslinking agent and heating may be performed simultaneously with the step of treating with a treatment liquid containing the water repellent composition described above. When performed simultaneously, for example, a treatment liquid containing the water repellent composition and the crosslinking agent is attached to the object to be treated, the water is removed, and then the crosslinking agent attached to the object to be treated is heated. Considering simplification of the water repellent treatment process, reduction of heat consumption, and economic efficiency, it is preferable to perform the step simultaneously with the treatment process of the water repellent composition.

[0147] Moreover, excessive use of the crosslinking agent may impair the feel. The crosslinking agent is preferably used in an amount of 0.1 to 50% by mass, particularly preferably 0.1 to 10% by mass, based on the material to be treated (textile product).

[0148] The water-repellent textile product of this embodiment obtained in this manner can exhibit sufficient water repellency even when used outdoors for a long period of time, and since the water-repellent textile product does not use any fluorine-based compounds, it can be environmentally friendly.

[0149] The water-repellent textile product of this embodiment can be coated on predetermined portions. Examples of coatings include moisture-permeable waterproofing and windproofing for sports and outdoor use. For example, moisture-permeable waterproofing can be achieved by applying a coating liquid containing a urethane resin, an acrylic resin, or the like and a medium to one side of the water-repellent textile product and drying it.

[0150] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0151] For example, in the case of producing a non-fluorinated polymer, the polymerization reaction is carried out by radical polymerization in the above embodiment, but the polymerization reaction may also be carried out by photopolymerization in which ionizing radiation such as ultraviolet rays, electron beams, or gamma rays is irradiated.

[0152] In the present invention, a textile product is treated with the non-fluorine-based water repellent composition to form a water-repellent textile product. However, the product to be treated with the non-fluorine-based water repellent composition is not limited to textile products, and may also be an article of metal, glass, resin, or the like.

[0153] In such cases, the method for applying the non-fluorinated water repellent composition to the article and the amount of the water repellent applied can be determined arbitrarily depending on the type of the article to be treated and other factors. [Example]

[0154] The present invention will be further explained below with reference to examples, but the present invention is not limited to these examples in any way.

[0155] <Preparation of water repellent aid> (Synthesis Example 1) A reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet, and dropping funnel was charged with 63.2 g of methyl hydrogen silicone with a SiH group equivalent weight of 63.2 g / mol and a degree of polymerization of 50. Nitrogen was introduced, and the mixture was heated to 65°C while mixing until homogeneous. A hydrosilylation catalyst, a solution of platinum(IV) chloride in ethylene glycol monobutyl ether and toluene, was added to the reaction system to achieve a platinum concentration of 5 ppm. When the reaction temperature reached 120°C, 168.3 g of 1 mole of 1-dodecene was added dropwise, and the reaction was continued at 120°C for 6 hours. Completion of the addition reaction was confirmed by FT-IR analysis of the resulting organo-modified silicone, confirming the disappearance of the absorption spectrum derived from the SiH group of the methyl hydrogen silicone. Thus, the organo-modified silicone represented by the general formula (1) above was prepared. 22 is a methyl group, R 23 is a dodecyl group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was used was obtained. 3 parts by mass of an ethylene oxide 9-mol adduct of a branched higher alcohol having 12 to 14 carbon atoms was added to 20 parts by mass of the obtained organo-modified silicone and mixed. 77 parts by mass of water was then added little by little while mixing, and emulsified in water to obtain a silicone emulsion.

[0156] (Synthesis Example 2) An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 84.2 g of 1 mole of 1-hexene was used instead of 168.3 g of 1 mole of 1-dodecene. The organo-modified silicone was a silicone emulsion represented by the general formula (1) above, where a is 0, b is 50, and R 22 is a methyl group, R 23is a hexyl group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was obtained.

[0157] (Synthesis Example 3) An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 252.5 g of 1 mole of 1-octadecene was used instead of 168.3 g of 1 mole of 1-dodecene. The organo-modified silicone was a silicone emulsion of general formula (1) where a is 0, b is 50, and R 22 is a methyl group, R 23 is an octadecyl group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was obtained.

[0158] (Synthesis Example 4) An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 84.2 g of 0.5 mol of 1-dodecene and 59.1 g of 0.5 mol of α-methylstyrene were used instead of 168.3 g of 1 mol of 1-dodecene. The organo-modified silicone was a silicone emulsion of general formula (1) where a is 0, b is 50, and R 22 is a methyl group, R 23 is a dodecyl group or a methylstyrene group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was obtained.

[0159] (Synthesis Example 5) An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 84.2 g of 0.5 moles of 1-dodecene and 126.2 g of 0.5 moles of 1-octadecene were used instead of 168.3 g of 1 mole of 1-dodecene. The organo-modified silicone was a silicone emulsion of general formula (1) where a is 0, b is 50, and R 22 is a methyl group, R 23 is a dodecyl group or an octadecyl group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was obtained.

[0160] (Synthesis Example 6) An organo-modified silicone and a silicone emulsion were obtained in the same manner as in Synthesis Example 1, except that 140.5 g of a copolymer of dimethylsiloxane and methylhydrogensiloxane, having a SiH group equivalent of 140.5 g / mol and a degree of polymerization of 50, was used instead of 63.2 g of methylhydrogensilicone, having a SiH group equivalent of 63.2 g / mol and a degree of polymerization of 50. The organo-modified silicone was a copolymer of general formula (1) in which a is 25, b is 25, and R 20 and R 21 is a methyl group, R 22 is a methyl group, R 23 is a dodecyl group, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 An organo-modified silicone in which the methyl group was obtained.

[0161] (Synthesis Example 7) To 20 parts by mass of hydrogen silicone (trade name: KF-99, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by mass of an ethylene oxide 9 mole adduct of a branched higher alcohol having 12 to 14 carbon atoms was added and mixed. Next, 77 parts by mass of water was added little by little while mixing, and emulsified in water to obtain a silicone emulsion.

[0162] (Synthesis Example 8) A silicone emulsion was obtained in the same manner as in Synthesis Example 7, except that dimethyl-modified silicone (trade name: KF-96H-300,000cs, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of hydrogen silicone.

[0163] <Preparation of polymer dispersion> Mixtures having the compositions shown in Tables 1 to 6 (in the tables, the numerical values ​​indicate (g)) were polymerized according to the procedure described below to obtain polymer dispersions.

[0164] (Synthesis Example 9) A 500 mL flask was charged with 60 g of stearyl acrylate, 2 g of Noigen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 2 g of Noigen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 3 g of stearyl dimethylamine hydrochloride, 25 g of tripropylene glycol, and 207.70 g of water, and the mixture was stirred at 45°C to form a mixed solution. Ultrasonic irradiation was performed on this mixed solution to emulsify and disperse all the monomers. Next, 0.3 g of azobis(isobutylamidine) dihydrochloride was added to the mixed solution, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere to obtain a non-fluorinated polymer dispersion with a polymer concentration of 20% by mass.

[0165] (Synthesis Examples 10 to 36) Polymerization was carried out in the same manner as in Synthesis Example 9 except that the materials shown in Tables 1 to 6 were used, to obtain non-fluorinated polymer dispersions having polymer concentrations shown in Tables 7 to 10, respectively.

[0166] It should be noted that it was confirmed by gas chromatography (GC-15APTF, manufactured by Shimadzu Corporation) that 98% or more of all monomers in each of the polymers in the polymer dispersions obtained in Synthesis Examples 9 to 36 had been polymerized.

[0167] Details of the materials shown in Tables 1 to 6 are as follows. Latemul PD-420 (Kao Corporation, polyoxyalkylene alkenyl ether, HLB=12.6) Latemul PD-430 (Kao Corporation, polyoxyalkylene alkenyl ether, HLB=14.4) Cardanol ethylene oxide 12.5 mole adduct (HLB=12.9, shown as "Cardanol 12.5EO" in the table) Cardanol ethylene oxide 8.3 mole adduct (HLB=11.0, shown as "Cardanol 8.3EO" in the table) Castor oil ethylene oxide 42 mole adduct (HLB=13.3, shown as "Castor oil 42EO" in the table) Castor oil with 30 moles of ethylene oxide (HLB=11.7, shown as "Castor oil 30EO" in the table)

[0168] In the table, "C8 fluoro group-containing acrylate" refers to a compound represented by the following general formula (III): [ka] The mixture is expressed as follows: where the average value of n is 8 (note that the mixture contains compounds where n is 6, 8, 10, 12, and 14).

[0169] The polymer dispersion obtained above and the polymer obtained by the method described below were evaluated.

[0170] (Evaluation of polymer properties) 500 mL of acetone was added to 50 g of the polymer dispersions obtained in Synthesis Examples 9 to 36 to separate the polymer and emulsifier, and the polymer was collected by filtration and dried under reduced pressure at 25°C for 24 hours. The obtained polymers were evaluated as follows. The results are shown in Tables 7 to 10.

[0171] (1) Melt viscosity measurement method The polymer obtained above was placed in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester CFT-500 (Shimadzu Corporation), 1 g of the polymer was held at 105°C for 6 minutes, and then the pressure was increased by the plunger to 100 kg·f / cm 2The melt viscosity was measured at 105°C by applying a load of 1000 kJ / min.

[0172] (2) Method for measuring weight-average molecular weight The weight-average molecular weight of the polymer obtained above was measured using a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation) under conditions of a column temperature of 40°C and a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent, and was measured in terms of standard polystyrene. Three columns, trade names TSK-GEL G5000HHR, G4000HHR, and G3000HHR manufactured by Tosoh Corporation, were connected and installed.

[0173] <Preparation of Water Repellent Composition> (Examples 1 to 37 and Comparative Examples 1 to 9) The water repellent auxiliaries (silicone emulsions) obtained in Synthesis Examples 1 to 8 and the polymer dispersions obtained in Synthesis Examples 9 to 36 were mixed in the mass ratios shown in Tables 11 to 15 to prepare water repellent compositions.

[0174] The water repellent composition obtained above was evaluated.

[0175] (Water repellency evaluation of textile products) The test was conducted according to the spray method of JIS L 1092 (1998) with a shower water temperature of 27°C. In this test, dyed 100% polyester fabric or 100% nylon fabric was immersed in a treatment solution prepared by diluting the water repellent compositions of the Examples and Comparative Examples with water to a polymer content of 3% by mass (pickup rate: 60% by mass), dried at 130°C for 2 minutes, and further heat-treated under the conditions shown in Tables 7 to 10. The water repellency of the resulting fabric was evaluated. The results were visually evaluated using the following scale. A "+" was assigned to slightly better properties, and a "-" was assigned to slightly worse properties. The results are shown in Tables 16 to 22. Water repellency: Condition 5: No adhesion or wetness on the surface 4: Slight adhesion and wetting on the surface 3: Shows partial surface wetting 2: Surface wetness 1: Shows wetting of the entire surface 0: Both sides are completely wet

[0176] (Feel evaluation of textile products) The feel was evaluated using dyed 100% polyester fabrics that were immersed in a treatment solution prepared by diluting the water repellent compositions of the Examples and Comparative Examples with water to a polymer content of 3% by mass (pickup rate: 60% by mass), dried at 130°C for 2 minutes, and then heat-treated at 170°C for 30 seconds. The results were evaluated using the following 5-point scale based on handling. The results are shown in Tables 16 to 22. 1: Hard ~ 5: Soft

[0177] (Evaluation of durable water repellency of textile products) The test was conducted according to the spray method of JIS L 1092 (1998) with the shower water temperature at 27 ° C. In this test, dyed 100% polyester fabric was immersed in a treatment solution prepared by diluting the water repellent compositions of the Examples and Comparative Examples and each of the above-mentioned agents with water so that the polymer content was 3% by mass, the content of UNIKA RESIN 380-K (crosslinking agent, manufactured by Union Chemical Industry Co., Ltd., trimethylol melamine resin) was 0.3% by mass, and the content of UNIKA CATALYST 3-P (surfactant, manufactured by Union Chemical Industry Co., Ltd., amino alcohol hydrochloride) was 0.2% by mass (pickup rate 60% by mass), and then dried at 130 ° C. for 2 minutes and further heat-treated at 170 ° C. for 60 seconds to obtain fabric (L-0). The water repellency of the fabric was also evaluated in the same manner as in the water repellency evaluation method described above after washing 10 times (L-10) according to the 103 method of JIS L 0217 (1995). Furthermore, the 100% nylon fabric was evaluated in the same manner as the 100% polyester fabric, except that the heat treatment temperature was changed from 170° C. to 160° C. The results are shown in Tables 16 to 22.

[0178] (peel strength of textile coatings) The test was conducted in accordance with JIS K 6404-5 (1999). In this test, dyed 100% nylon fabric was immersed (pickup rate: 60% by mass) in a treatment solution prepared by diluting the water repellent compositions of the Examples and Comparative Examples with water to a polymer content of 3% by mass. The fabric was then dried at 130°C for 2 minutes and heat-treated at 160°C for 30 seconds to obtain a base fabric. A hot-melt adhesive tape ("MELCO Tape" manufactured by Sun Chemical Industry Co., Ltd.) was thermally bonded to the resulting base fabric at 150°C for 1 minute using a thermocompression bonding device, and the peel strength between the base fabric and the seam tape was measured using an autograph (AG-IS manufactured by Shimadzu Corporation). The gripper was pulled at a moving speed of 100 mm / min, and the average stress was recorded as the peel strength [N / inch]. The results are shown in Tables 16 to 22.

[0179] [Table 1]

[0180] [Table 2]

[0181] [Table 3]

[0182] [Table 4]

[0183] [Table 5]

[0184] [Table 6]

[0185] [Table 7]

[0186] Table 8

[0187] Table 9

[0188] Table 10

[0189] Table 11

[0190] Table 12

[0191] Table 13

[0192] Table 14

[0193] Table 15

[0194] Table 16

[0195] Table 17

[0196] [Table 18]

[0197] [Table 19]

[0198] [Table 20]

[0199] [Table 21]

[0200] [Table 22]

[0201] It was confirmed that the textile products treated with the water repellent compositions of Examples 1 to 37 exhibited water repellency equal to or greater than that of the textile products treated with a conventional fluorine-based water repellent (Comparative Example 7) and the textile products treated with only the organo-modified silicone represented by the general formula (1) (Comparative Example 8), even without heat treatment, and that they had excellent durable water repellency and a good feel.

[0202] Furthermore, it was confirmed that the textile products treated with the water repellent compositions of Examples 1 to 37 exhibited water repellency equal to or greater than that of the textile products treated with the water repellent composition (Comparative Example 9) that did not contain the organo-modified silicone represented by the general formula (1), and had excellent durable water repellency and superior peel strength against resin coatings.

[0203] The water repellent compositions of Comparative Examples 1 to 6 used silicones other than the organo-modified silicone represented by the general formula (1) above, and tended to be particularly inferior in durable water repellency.

Claims

1. A water repellent aid and a non-fluorine-based water repellent agent are included, The water repellent aid contains an organo-modified silicone represented by the following general formula (1): the non-fluorine-based water repellent agent comprises a non-fluorine-based polymer containing a structural unit derived from a (meth)acrylic acid ester monomer (A) represented by the following general formula (A-1), the total constituent ratio of the (meth)acrylic acid ester monomer (A) represented by general formula (A-1) in the non-fluorine-based polymer is 50% by mass to 100% by mass based on the total amount of monomer components constituting the non-fluorine-based polymer, The non-fluorine-containing water repellent composition, wherein the non-fluorine-containing polymer further contains a structural unit derived from at least one monomer (E) of vinyl chloride or vinylidene chloride. 【Chemistry 1】 [In formula (1), R ２０ , R ２１ and R ２２ each independently represents a methyl group; R ２３ represents a methylstyrene group or an alkyl group having 6 to 22 carbon atoms, and R ３０ , R ３１ , R ３２ , R ３３ , R ３４ and R ３５ each independently represents a methyl group, a represents an integer of 0 to 30, b represents an integer of 1 or more, (a+b) is 40 to 60, and when a is 2 or more, a plurality of R ２０ and R ２１ may be the same or different, and multiple R ２２ and R ２３ may be the same or different. 【Chemistry 2】 [In formula (A-1), R １ represents hydrogen or a methyl group, R ２ represents a monovalent hydrocarbon group having 12 to 24 carbon atoms which may have a substituent.]

2. 2. The non-fluorinated water repellent composition according to claim 1, wherein the non-fluorinated polymer further contains a structural unit derived from at least one reactive emulsifier (B) selected from the group consisting of: (B1) a compound represented by the following general formula (I-1) having an HLB of 7 to 18; (B2) a compound represented by the following general formula (II-1) having an HLB of 7 to 18; and (B3) a compound formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, the compound having an HLB of 7 to 18. 【Transformation 3】 [In formula (I-1), R ３ represents hydrogen or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, Y １ represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 【Chemistry 4】 [In formula (II-1), R ４ represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group; Y ２ represents a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

3. 3. The non-fluorine-containing water repellent composition according to claim 1, wherein the non-fluorine-containing polymer further contains a structural unit derived from at least one second (meth)acrylic acid ester monomer (C) selected from the group consisting of (C1) a (meth)acrylic acid ester monomer represented by the following general formula (C-1), (C2) a (meth)acrylic acid ester monomer represented by the following general formula (C-2), (C3) a methacrylic acid ester monomer represented by the following general formula (C-3), (C4) a (meth)acrylic acid ester monomer represented by the following general formula (C-4), and (C5) a (meth)acrylic acid ester monomer represented by the following general formula (C-5): 【Transformation 5】 [In formula (C-1), R ５ represents hydrogen or a methyl group, R ６ represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less. However, the above (C5) (meth)acrylic acid ester monomer represented by the following general formula (C-5) is not included.] 【Transformation 6】 [In formula (C-2), R ７ represents hydrogen or a methyl group, R ８ represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.] 【Transformation 7】 [In formula (C-3), R ９ represents an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.] 【Transformation 8】 [In formula (C-4), R １０ represents hydrogen or a methyl group, p represents an integer of 2 or greater, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group. 【Chemistry 9】 [In formula (C-5), R １１ represents hydrogen or a methyl group, R １２ represents a monovalent chain saturated hydrocarbon group having 3 to 6 carbon atoms and having a hydroxyl group and at least one functional group selected from the group consisting of a chloro group and a bromo group.

4. The (meth)acrylic acid ester monomer (A) represented by the general formula (A-1) is R １ is hydrogen, and １ The non-fluorine-containing water repellent composition according to any one of claims 1 to 3, comprising a methacrylic acid ester monomer (a2) in which is a methyl group.

5. 5. The non-fluorine-containing water repellent composition according to claim 1, wherein the content of the organo-modified silicone is 1 to 50 parts by mass per 100 parts by mass of the non-fluorine-containing polymer.

6. The non-fluorine-based water repellent composition according to any one of claims 1 to 5, which is for use on a fiber containing polyester.

7. A method for producing a water-repellent textile product, comprising a step of treating a textile product with a treatment liquid containing the non-fluorinated water repellent composition according to any one of claims 1 to 6.

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