dispersion

Abstract

To provide a fiber surface treatment agent capable of imparting, to a fiber product, excellent characteristics in an overall view, with regard to water repellency, washing durability of the water repellency and seam smoothness even without containing fluorine.SOLUTION: A fiber surface treatment agent at least includes a constituent A, a constituent B, and water, and is an aqueous emulsion dispersion not containing a fluorine atom. The constituent A is a polymer having at least one kind of monomer with a glass transition point 50°C or higher in a homopolymer as a repeating unit. The constituent A is included by 12 to 60 mass% based on a total 100 mass% of the constituent A and the constituent B in the aqueous emulsion dispersion. In the aqueous emulsion dispersion, an average particle diameter of a dispersion containing the constituent A is smaller than 3.0 μm. The constituent B is at least one kind from prescribed hydrophobic compounds B1, B2 and B3.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a surface treatment agent for fibers. A dispersion used as an additive to improve suture slippage.

Background Art

[0002] As a method for imparting water repellency to fiber products, water repellent treatment with an aqueous emulsion dispersion such as paraffin wax, silicone resin, or fluororesin is known. Since fluororesin exhibits better water repellency than paraffin wax or silicone resin, it is widely used for the water repellent treatment of fiber products.

[0003] However, in 2000, the harmful effects, bioaccumulation, and environmental pollution of perfluorooctanesulfonic acid (PFOS) were pointed out, and further concerns were raised about all perfluorinated compounds having 8 or more carbon atoms including perfluorooctanoic acid (PFOA). For this reason, development of fluorine-based water repellent treatment agents that do not contain these fluorine compounds and do not generate any concerning decomposition products has been carried out.

[0004] However, in recent years, the harmful effects and environmental pollution of compounds themselves having a perfluoroalkyl group, regardless of the number of carbon atoms, have been pointed out. Therefore, in the field of water repellent treatment for fiber products, there is a movement to stop using water repellent treatment agents containing fluorine.

[0005] Conventionally, compositions using paraffin wax, silicone resin, etc. are known as water repellent treatment agents that do not contain fluorine. However, the water repellency of these compositions was inferior compared to water repellent treatment agents using fluororesin. Under such circumstances, an aqueous emulsion dispersion of a (meth)acrylate polymer having an alkyl group with 12 or more carbon atoms in the ester moiety has been proposed as an alternative to water repellent treatment agents using fluororesin (Patent Document 1).

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent Publication No. 2006-328624 [Patent Document 2] Special Publication No. 2012-522062 [Overview of the project] [Problems that the invention aims to solve]

[0007] In recent years, in textile products with excellent water-repellent durability against washing and other processes, there has been a demand for the use of finer fibers, ranging from approximately 55-110 dtex (50-100 d) to approximately 11-44 dtex (10-40 d), prioritizing lightness and texture. However, when fine fibers of approximately 11-44 dtex are treated with a water-repellent agent mainly composed of alkyl (meth)acrylate, as described in Patent Document 1, there has been a tendency for seam slippage in the textile product to become extremely large. This has resulted in problems such as misalignment of stitches and seams during sewing and wearing. Furthermore, even when paraffin wax, as disclosed in Patent Document 2, was incorporated, it was not possible to reduce seam slippage.

[0008] Furthermore, copolymers mainly composed of alkyl (meth)acrylate, such as those described in Patent Document 1, have poor emulsification stability even when appropriate surfactants are used. This can lead to emulsification failure during fiber processing, causing problems such as resin adhering to processing equipment and treated fabrics.

[0009] Under these circumstances, the present invention relates to fluorine By adding it to a surface treatment agent for fibers that does not contain atoms, sewing About eye slippage , Yu These properties can be imparted to textile products. dispersion The primary purpose is to provide. [Means for solving the problem]

[0010] The present inventors conducted diligent research to solve the aforementioned problems. As a result, they found that a surface treatment agent for textiles can be obtained that, despite not containing fluorine, can impart overall superior properties to textile products in terms of water repellency, the wash durability of said water repellency, and seam slippage, to textile products. The present invention provides an aqueous emulsion dispersion containing at least component A, component B, and water, and does not contain fluorine atoms, wherein component A is a polymer having at least one monomer whose glass transition temperature is 50°C or higher as a repeating unit, component A is present in an aqueous emulsion dispersion in an amount of 12 to 60% by mass relative to 100% by mass of the total of components A and B, the average particle size of the dispersion containing component A is less than 3.0 μm, and component B is at least one of the hydrophobic compounds B1, B2, and B3 described below.

[0011] Hydrophobic compound B1: A polymer having at least one monoethylene unsaturated monomer b represented by the following general formula (1) as a repeating unit. [ka]

[0012] [In general formula (1), R 11 R is a hydrogen atom, a methyl group, or a chloro group. 12 It is a saturated aliphatic hydrocarbon group with 16 to 30 carbon atoms.

[0013] Hydrophobic compound B2: A silicone compound, which is a polymer represented by the following general formula (2). [ka]

[0014] [In general formula (2), R 21 and R 24 Each of these is independently a hydrogen atom, a carbon-1 to carbon-4 alkoxy group, or a trialkylsilyl group having each independently of a carbon-1 to carbon-4 alkyl group, and R22 is an alkyl group having 1 to 32 carbon atoms, R 23 is an organic group having 1 to 9 carbon atoms and having at least one amino group, n 21 and n 22 are each independently an integer from 1 to 100.]

[0015] Hydrophobic compound B3: A composition having an alcohol represented by the following general formula (3) and a blocked isocyanate in the same particle, a reaction product of the alcohol and a polyisocyanate, and a reaction product of a partial reaction product of the alcohol and a polyisocyanate and a blocking agent At least one selected from the group consisting of [Chemical formula]

[0016] [In general formula (2), n 31 is an integer from 3 to 8, n 31 -n 32 is an integer from 1 to 7, n 32 is an integer from 1 to 7, R 31 is a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms or an acyl group having a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms, and A is a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 3 to 6 carbon atoms and 3 to 6 valences, a residue obtained by removing a hydroxyl group from a dimer to trimer of the polyhydric alcohol, and a residue obtained by removing a hydroxyl group from an intramolecular dehydration cyclized product of a 5 to 6 valent polyhydric alcohol At least one selected from the group consisting of

[0017] The present invention has been completed by further studies based on these findings.

[0018] That is, the present invention has the following aspects. Item 1. An aqueous emulsion dispersion containing at least component A, component B, and water, and not containing a fluorine atom, The component A is a polymer having at least one monomer having a glass transition point of the homopolymer of 50°C or higher as a repeating unit, Component A is present in the aqueous emulsion dispersion at an amount of 12 to 60% by mass relative to the total mass of component A and component B, which is 100% by mass. In the aqueous emulsion dispersion, the average particle size of the dispersion containing component A is less than 3.0 μm. The aforementioned component B is at least one of the hydrophobic compounds B1, B2, and B3 described below, in a surface treatment agent for textiles. Hydrophobic compound B1: A polymer having at least one monoethylene unsaturated monomer b represented by the following general formula (1) as a repeating unit. [ka] [In general formula (1), R 11 R is a hydrogen atom, a methyl group, or a chloro group. 12 It is a saturated aliphatic hydrocarbon group with 16 to 30 carbon atoms. Hydrophobic compound B2: A silicone compound, which is a polymer represented by the following general formula (2). [ka] [In general formula (2), R 21 and R 24 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a trialkylsilyl group having each of the independently C1-C4 alkyl groups, R 22 R is an alkyl group having 1 to 32 carbon atoms. 23 is an organic group having 1 to 9 carbon atoms and having at least one amino group, n 21 and n 22 Each of these is an integer between 1 and 100, independently of the others. Hydrophobic compound B3: At least one selected from the group consisting of a composition having an alcohol represented by the following general formula (3) and a polyblocked isocyanate in the same particle, a reaction product of the alcohol and the polyisocyanate, and a reaction product of the alcohol and a blocking agent that can react with the isocyanate group and the polyisocyanate. [ka] [In general formula (3), n 31 n is an integer between 3 and 8. 31 -n 32 n is an integer from 1 to 7, and n 32 is an integer from 1 to 7, and R 31 A is a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms or an acyl group having a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms, and A is at least one selected from the group consisting of a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 6 or less carbon atoms with a 3-6 valency, a residue obtained by removing a hydroxyl group from a dimer or trimer of the said polyhydric alcohol, and a residue obtained by removing a hydroxyl group from an intramolecular dehydrated cyclized product of a polyhydric alcohol with a 5-6 valency. Item 2. The surface treatment agent for fibers according to Item 1, wherein the monomer in component A, whose homopolymer has a glass transition temperature of 50°C or higher, is at least one of monoethylene unsaturated monomers a represented by the following general formula (4). [ka] [In general formula (4), R 41 is a hydrogen atom, a methyl group, or a chloro group, n 41 n is an integer of 0 or 1, and n 41 When R is 0, 42 n is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups, 41 1, R 41 When R is a methyl group or a chloro group, 42 is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups; a phenyl or benzyl group, which may have one or more chloro or bromo groups; or a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, n 41 1, R 41 When R is a hydrogen atom, 42 This is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups. Item 3. The surface treatment agent for fibers according to Item 1 or 2, wherein in component A, monomer a is at least one selected from the group consisting of a monoethylene unsaturated monomer a1 having a styrene skeleton represented by the following general formula (5), a monoethylene unsaturated monomer a2 having a cyclic aliphatic skeleton represented by the following general formula (6), and another monoethylene unsaturated monomer a3 represented by the following general formula (7). [ka] [In general formula (5), R 51 R is a hydrogen atom, a methyl group, or a chloro group. 52 and R 53 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a chloro group, or a chloromethyl group. [ka] [In general formula (6), R 54 R is a hydrogen atom, a methyl group, or a chloro group. 55 This is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups. [ka] [In general formula (7), R 56 R is a methyl group or a chloro group, 57 This is a methyl group, an ethyl group, or a tert-butyl group. Item 4. The surface treatment agent for fibers according to Item 3, wherein in component A, the total proportion of monomer a1, monomer a2, and monomer a3 is 55% by mass or more. Item 5. The surface treatment agent for fibers according to any one of items 1 to 4, wherein the monomer constituting the polymer of component A further comprises a monoethylenically unsaturated monomer c having at least one of a (meth)acryloyl group and a vinyl group and a polyoxyethylene group. Item 6. A surface treatment agent for fibers according to any one of items 1 to 5, wherein the monomer constituting the polymer of component A further comprises a crosslinkable ethylenically unsaturated monomer d having at least one selected from the group consisting of a hydroxyl group, epoxy group, acetoacetyl group, carbonyl group, chloromethyl group, amide group, N-alkoxymethylamide group, blocked isocyanate group, oxazoline group, carboxyl group, sulfonic acid group, and alkoxysilyl group. Item 7. The surface treatment agent for fibers according to any one of items 1 to 6, wherein the aqueous emulsion dispersion contains particles in which component A and component B are present in the same particle. Item 8. The surface treatment agent for fibers according to any one of items 1 to 7, wherein the aqueous emulsion dispersion comprises particles composed of component A and particles composed of component B. Item 9. A textile product having its fiber surface treated with a surface treatment agent for textiles described in any of Items 1 to 8. [Effects of the Invention]

[0019] According to the present invention, fluorine By adding it to a surface treatment agent for fibers that does not contain atoms, sewing About eye slippage , Yu These properties can be imparted to textile products. dispersion We can provide this. [Modes for carrying out the invention]

[0020] In this specification, "(meth)acrylate" means "acrylate or methacrylate," and the same applies to other similar expressions.

[0021] In this specification, the glass transition temperature of homopolymers is the value described in the literature (Polymer Handbook Third Edition, published in 1990 by John Wiley & Sons). For monomers for which the glass transition temperature is not described in the literature, the homopolymer is synthesized (with a weight-average molecular weight in the range of 10,000 to 10,000,000 by GPC), and the value measured by differential scanning calorimeter (DSC) is adopted.

[0022] In this specification, "fluorine atom-free" for textile surface treatment agents means that when the textile surface treatment agent is subjected to fluorine analysis (combustion-ion chromatography), the fluorine atom content is below the detection limit (50 ppm or less).

[0023] In this specification, the average particle size of the aqueous emulsion dispersion of component A is the arithmetic mean diameter (D50) measured using a laser diffraction / scattering particle size distribution analyzer LA-300 (manufactured by Horiba, Ltd.).

[0024] In this specification, "emulsified dispersion" means an emulsion or dispersion in a medium.

[0025] (Surface treatment agent for textiles) The fluorine atom-free surface treatment agent for fibers of the present invention is an aqueous emulsion dispersion containing at least component A, component B, and water, wherein component A is a polymer having at least one monomer whose homopolymer glass transition temperature is 50°C or higher as a repeating unit, and component A is present in the aqueous emulsion dispersion at an amount of 12 to 60% by mass relative to 100% by mass of the total of component A and component B, and in the aqueous emulsion dispersion, the average particle size of the dispersion containing component A (dispersed particles containing component A) is less than 3.0 μm, and component B is at least one of the hydrophobic compounds B1, B2, and B3, and is provided in the form of an aqueous emulsion dispersion containing a surfactant and additives as needed.

[0026] (Component A) Component A is a polymer having at least one monomer as a repeating unit, the homopolymer having a glass transition temperature of 50°C or higher. Hereinafter, the monomers constituting the polymer of component A may be referred to as monomers contained in component A. The same applies to the monomers constituting the polymer of component B. Examples of monomers having a glass transition temperature of 50°C or higher include ethylenically unsaturated monomers that can undergo addition polymerization, and monoethylenically unsaturated monomers having one ethylenically unsaturated group in one molecule are preferred. An example of component A is a polymer having at least one monoethylenically unsaturated monomer a represented by the following general formula (4) as a repeating unit, the homopolymer having a glass transition temperature of 50°C or higher.

[0027] [ka]

[0028] [In general formula (4), R 41 is a hydrogen atom, a methyl group, or a chloro group, n 41 n is an integer of 0 or 1, and n 41 When R is 0, 42 n is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups, 41 1, R 41 When R is a methyl group or a chloro group, 42 n is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups, or a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, 41 1, R 41 When R is a hydrogen atom, 42 This is a cyclic hydrocarbon group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups.

[0029] R 41 Examples include hydrogen atoms, methyl groups, or chloro groups. 41 When R is 0, 41 It is preferable that n is a hydrogen atom.41 1 is R 41 When R is a methyl group or a chloro group, 42 Preferably, n is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups; a phenyl or benzyl group having one or more chloro or bromo groups; or a saturated aliphatic hydrocarbon group having 4 or fewer carbon atoms. 41 1 is R 41 When R is a hydrogen atom, 42 Preferably, the group is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups, or a phenyl or benzyl group, which may have one or more chloro or bromo groups.

[0030] R 42 The cyclic aliphatic group having less than 16 carbon atoms may or may not have a chloro group, a bromo group, or a chloromethyl group, but from the viewpoint of manufacturing or availability of monomer a, it is preferable that it does not have the aforementioned functional groups. The cyclic aliphatic group having less than 16 carbon atoms is preferably a cyclic aliphatic group having one of the following skeletons: cyclopentanyl skeleton, cyclohexyl skeleton, isobolonyl skeleton, adamantyl skeleton, or dicyclopentanyl skeleton. The phenyl group or benzyl group which may have one or more chloro groups or bromo groups may or may not have a chloro group or a bromo group, and the number of substitutions may be any number from 1 to 5. The saturated aliphatic hydrocarbon group having 4 carbon atoms or less is preferably a methyl group, an ethyl group, or a tert-butyl group.

[0031] From the viewpoint of imparting overall superior properties to textile products in the aforementioned respects, in component A, the proportion of monomer a is preferably more than 55% by mass, more preferably 65% ​​by mass or more, and even more preferably 75% by mass or more, and the upper limit is preferably 100% by mass or less, 95% by mass or less, 90% by mass or less, etc.

[0032] The monomer a contained in component A is not particularly limited as long as the glass transition temperature of the homopolymer is 50°C or higher. However, from the viewpoint of imparting superior overall properties to textile products in terms of water repellency, wash durability of said water repellency, and seam slippage, the lower limit of the glass transition temperature is preferably 60°C or higher, more preferably 70°C or higher. The upper limit is not particularly limited, but from a manufacturing viewpoint, 200°C or lower is preferred.

[0033] From the viewpoint of imparting overall superior properties to textile products in the aforementioned respects, examples of monomer a include monoethylene unsaturated monomer a1 having a styrene skeleton represented by the following general formula (5), monoethylene unsaturated monomer a2 having a cyclic aliphatic skeleton represented by the following general formula (6), and other monoethylene unsaturated monomer a3 (different from monomers a1 and a2) represented by the following general formula (7).

[0034] [ka]

[0035] [In general formula (5), R 51 R is a hydrogen atom, a methyl group, or a chloro group. 52 and R 53 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a chloro group, or a chloromethyl group.

[0036] [ka]

[0037] [In general formula (6), R 54 R is a hydrogen atom, a methyl group, or a chloro group. 55 This is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups.

[0038] [ka]

[0039] [In general formula (7), R 56 R is a methyl group or a chloro group, 57 This is a methyl group, an ethyl group, or a tert-butyl group.

[0040] In monomer a1, R 51 is a hydrogen atom, a methyl group, or a chloro group, and is preferably a hydrogen atom. In monomer a1, R 52 and R 53 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a chloro group, or a chloromethyl group, and R 52 and R 53 Preferably, one of them is a hydrogen atom.

[0041] Specific examples of monomer a1 include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, chlorostyrene, and chloromethylstyrene. Monomer a1 may consist of only one type or two or more types.

[0042] In monomer a2, R 54 R is a hydrogen atom, a methyl group, or a chloro group, with a methyl group or a chloro group being preferred. In monomer a2, 55 R is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups. The cyclic aliphatic group having less than 16 carbon atoms may or may not have a chloro, bromo, or chloromethyl group, but from the viewpoint of manufacturing or obtaining monomer a2, it is preferable that it does not have the aforementioned functional groups. 55 The cyclic aliphatic group having fewer than 16 carbon atoms is preferably a cyclic aliphatic group having one of the following skeletons: cyclopentanyl skeleton, cyclohexyl skeleton, isoboronyl skeleton, adamantyl skeleton, or dicyclopentanyl skeleton, and is particularly preferred to have one of the following skeletons: cyclohexyl skeleton, isoboronyl skeleton, or dicyclopentanyl skeleton.

[0043] Specific examples of monomer a2 include cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, isobolonyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyladamantyl (meth)acrylate, 2-ethyladamantyl (meth)acrylate, tricyclopentanyl (meth)acrylate, cyclohexyl α-chloroacrylate, tert-butyl α-chlorocyclohexyl acrylate, isobolonyl α-chloroacrylate, dicyclopentenyl α-chloroacrylate, dicyclopentanyl α-chloroacrylate, adamantyl α-chloroacrylate, 2-methyladamantyl α-chloroacrylate, 2-ethyladamantyl α-chloroacrylate, and tricyclopentanyl α-chloroacrylate. Monomer a2 may be one type or two or more types.

[0044] In monomer a3, R 56 R is a methyl group or a chloro group, 57 The group is a methyl group, an ethyl group, or a tert-butyl group, and is not particularly limited.

[0045] Specific examples of monomer a3 include methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, methyl α-chloroacrylate, ethyl α-chloroacrylate, and tert-butyl α-chloroacrylate. Monomer a3 may be of one type or two or more types.

[0046] Furthermore, component A may optionally contain a monoethylene unsaturated monomer c different from monomers a1, a2, and a3. Monomer c is a monomer having at least one of a (meth)acryloyl group and a vinyl group and a polyoxyethylene group. Monomer c may also have a (poly)oxyalkylene group consisting of an alkylene group having 3 to 10 carbon atoms, in addition to the polyoxyethylene group. Monomer c contributes to improving the emulsion dispersion stability in the aqueous emulsion dispersion of component A. Specific examples of monomer c include polyoxyoxyalkylene alkenyl ethers and polyoxyalkylene (meth)acrylates.

[0047] Specific examples of monomer c include Latemul PD-420, Latemul PD-430, Latemul PD-450 manufactured by Kao Corporation, and Uniox PKA-5001, Uniox PKA-5002, Uniox PKA-5003, Uniox PKA-5004, Uniox PKA-5005, Uniox PKA-5006, Uniox PKA-5007, Uniox PKA-5008, Uniox PKA-5009, Uniox PKA-5010, Unisafe PKA-5011, and Unisafe manufactured by NOF Corporation. PKA-5012, Unilube PKA-5013, Unisafe PKA-5015, Unisafe PKA-5016, Unisafe PKA-5017, Bremmer PE-90, Bremmer PE-200, Bremmer PE-350, Bremmer 50PEP-300, Bremmer 70PEP-350B, Bremmer 55PET-800, Bremmer AE-90U, Bremmer AE-200, Bremmer AE-400, Bremmer PME-100, Bremmer PME-200, Bremmer PME-400, Bremmer PME-1000, Bremmer PME-4000, Bremmer 50POEP-800B, Bremmer PLE-200, Bremmer PLE-1300, Examples include Remmer PSE-1300, Bremmer 43PAPE-600B, Bremmer AME-400, Bremmer ALE-200, Bremmer 75ANEP-600, Bremmer AAE-300, Adekaria Soap ER-10, Adekaria Soap ER-20, Adekaria Soap ER-30, Adekaria Soap NE-10, Adekaria Soap NE-20, Adekaria Soap NE-30 from ADEKA Corporation, Aqualon RN-20, Aqualon RN-2025, Aqualon RN-30, Aqualon RN-50 from Daiichi Kogyo Seiyaku Co., Ltd., and Antox LMA-10, Antox LMA-20, Antox LMA-27 from Nippon Emulsifier Co., Ltd.

[0048] With respect to monomer c, the glass transition temperature of the homopolymer may be 50°C or higher, or it may be less than 50°C.

[0049] When component A contains monomer c, from the viewpoint of imparting overall superior properties to the textile product in the aforementioned respects, the upper limit of its content is preferably 10% by mass or less, more preferably 9% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more.

[0050] Furthermore, component A may optionally contain an ethylenically unsaturated monomer d different from monomers a1, a2, a3 and monomer c. Monomer d is a monomer having a crosslinkable functional group. Examples of the crosslinkable functional group include a hydroxyl group, epoxy group, acetoacetyl group, carbonyl group, chloromethyl group, amide group, N-alkoxymethylamide group, blocked isocyanate group, oxazoline group, carboxyl group, sulfonic acid group, and alkoxysilyl group, with hydroxyl group, epoxy group, acetoacetyl group, carbonyl group, chloromethyl group, amide group, N-alkoxymethylamide group, and blocked isocyanate group being preferred, and hydroxyl group, epoxy group, acetoacetyl group, N-alkoxymethylamide group, and blocked isocyanate group being particularly preferred.

[0051] The monomer d is preferably (meth)acrylates, acrylamides, vinyl ethers, or vinyl esters.

[0052] The presence of monomer d contributes to the adhesion of component A to the fibers, thereby suppressing shedding during washing.

[0053] Preferred specific examples of monomer d include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polycaprolactone ester of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, diacetone (meth)acrylamide, monocrystalline hydroxypropyl Examples include vinyl loroxate, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl(meth)acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl(meth)acrylate, phenylglycidylethyl acrylate tolylene diisocyanate, and 3-(methylethyl ketoxime)isocyanatomethyl-3,5,5-trimethylcyclohexyl(2-hydroxyethyl methacrylate)cyanate.

[0054] With respect to monomer d, the glass transition temperature of the homopolymer may be 50°C or higher, or it may be less than 50°C.

[0055] When component A contains monomer d, the upper limit of its content is preferably 4% by mass or less, more preferably 3% by mass or less, and the lower limit is preferably 0.3% by mass or more, more preferably 0.6% by mass or more.

[0056] Furthermore, component A may optionally contain an ethylenically unsaturated monomer e different from monomers a1, a2, a3 and monomers c and d. Monomer e is an alkyl (meth)acrylate ester in which the hydrocarbon groups of the ester portion are linear or branched, and is copolymerizable with monomer a and at least one of monomers c and d. In addition, the glass transition temperature of the homopolymer of monomer e is less than 50°C. Monomer e contributes to suppressing the increase in particle size of the aqueous emulsion dispersion of component A.

[0057] Specific examples of monomer e include methyl acrylate, ethyl acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, 2-octyldodecyl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

[0058] When component A contains monomer e, the upper limit of its content is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0059] Furthermore, component A may optionally contain an ethylenically unsaturated monomer f different from monomers a1, a2, a3 and monomers c, d, e.

[0060] Examples of monomer f include ethylene, propylene, butene, isoprene, butadiene, piperylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, chloroprene, vinyl chloride, vinylidene chloride, alkyl crotonate, alkyl maleate, alkyl fumarate, alkyl itaconate, alkyl citraconate, alkyl mesaconate, and the like. Monomer f is not limited to these examples.

[0061] When component A contains monomer f, the upper limit of its content is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0062] (Component B) Component B is at least one of the following three hydrophobic compounds: B1, B2, and B3. Component B may consist of only one of the hydrophobic compounds B1, B2, and B3, or two or more.

[0063] (Hydrophobic compound B1) Hydrophobic compound B1 is a polymer that has at least one monoethylene unsaturated monomer b, represented by the following general formula (1), as a repeating unit. [ka] [In the formula, R 11 R is a hydrogen atom, a methyl group, or a chloro group. 12 It is a saturated aliphatic hydrocarbon group with 16 to 30 carbon atoms.

[0064] In monomer b, R 12 It is preferable that the hydrocarbon group is a linear hydrocarbon group, and more preferably that the hydrocarbon group has 18 to 30 carbon atoms. The hydrocarbon group may be saturated or unsaturated, but it is preferable that it be a saturated aliphatic hydrocarbon group. Also, R 11 The monomer may be a hydrogen atom, a methyl group, or a chloro group, but (α-chloro)acrylate monomers are preferred from the viewpoint of water repellency. Furthermore, (meth)acrylate monomers are preferred from the viewpoint of the texture of the textile product after treatment.

[0065] Preferred specific examples of monomer b include (meth)cetyl acrylate, (meth)heptadecyl acrylate, (meth)stearyl acrylate, (meth)nonadecyl acrylate, (meth)icosyl acrylate, (meth)henicosyl acrylate, (meth)behenyl acrylate, (meth)tetracosyl acrylate, (meth)hexacosyl acrylate, and (meth)triacontyl acrylate.

[0066] Furthermore, the hydrophobic compound B1 may optionally contain a monoethylenically unsaturated monomer g having an organopolysiloxane skeleton.

[0067] In monomer g, the ethylenically unsaturated group is one of a vinyl group, a styryl group, or a (meth)acryloyl group, and the (meth)acryloyl group is preferred due to its ease of copolymerization, ease of synthesis, and availability as a commercially available product.

[0068] Preferred examples of monomer g include X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, and X-22-2404 from Shin-Etsu Chemical Co., Ltd., and Sylahplane FM-0711, Sylahplane FM-0721, Sylahplane FM-0725, and Sylahplane TM-0701T from JNC Corporation.

[0069] The presence of monomer g improves the water repellency and water-repellent durability during washing in the hydrophobic compound B1.

[0070] When the monomer g is included in the hydrophobic compound B1, from the viewpoint of imparting overall superior properties to the textile product in the aforementioned respects, the content thereof is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less, relative to the total amount of hydrophobic compound B1, with no particular limit on the lower limit.

[0071] Furthermore, the hydrophobic compound B1 may optionally contain monomer c. Unless otherwise specified, monomer c is as described above. In the aqueous emulsion dispersion of hydrophobic compound B1, monomer c contributes to improving the emulsion dispersion stability.

[0072] When the monomer c is included in the hydrophobic compound B1, from the viewpoint of imparting overall superior properties to the textile product in the aforementioned respects, the upper limit of its content is preferably 10% by mass or less, more preferably 9% by mass or less, and the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more.

[0073] Furthermore, the hydrophobic compound B1 may optionally contain monomer d. Unless otherwise specified, monomer d is the same as described above. The presence of monomer d contributes to the adhesion to fibers in the hydrophobic compound B1, improving the water-repellent properties and wash durability.

[0074] When monomer d is included in hydrophobic compound B1, the content of monomer d is preferably 4% by mass or less, more preferably 3% by mass or less, and preferably 0.3% by mass or more, more preferably 0.6% by mass or more, relative to the total amount of hydrophobic compound B1.

[0075] Furthermore, the hydrophobic compound B1 may optionally contain an ethylenically unsaturated monomer h different from monomers b, c, d and monomer g.

[0076] Examples of monomer h include vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ethers, acrylonitrile, alkylolacrylamide, alkyl crotonate, alkyl maleate, alkyl fumarate, alkyl itaconate, alkyl citraconate, and alkyl mesaconate. Monomer h is not limited to these examples.

[0077] When the monomer h is contained in the hydrophobic compound B1, the upper limit of its content is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0078] (Hydrophobic compound B2) Hydrophobic compound B2 is a silicone compound, which is a polymer represented by the following general formula (2). [ka]

[0079] [In general formula (2), R 21 and R 24is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a trialkylsilyl group having independently an alkyl group having 1 to 4 carbon atoms each, or an organic group having 1 to 9 carbon atoms and having at least one amino group, and R 22 is an alkyl group having 1 to 32 carbon atoms, and R 23 is an organic group having 1 to 9 carbon atoms and having at least one amino group, and n 21 and n 22 are each independently an integer of 1 to 100.]

[0080] Examples of the hydrophobic compound B2 include amino-modified silicones, those in which an amino group is introduced into the side chain of the siloxane structure, those in which an amino group is introduced into the end of the siloxane structure, and any of these mixtures may be used. As the amino group, a monoamine, a diamine, or a partially blocked one may be used. In the amino-modified silicone, from the viewpoint of hydrophobicity, it is preferable to use one having an amine equivalent of about 300 to 20,000 g / mol, and more preferably 1,000 to 20,000 g / mol when considering hydrophobicity, washing durability, texture, price, etc. Such amino-modified silicones can be selected from commercially available products. For example, WACKER FINISH WR301, WR4100, WR4200, WR1300, WR1600 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., KF-867, KF-869, KF-8004 manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be used.

[0081] (Hydrophobic compound B3) The hydrophobic compound B3 is at least one selected from the group consisting of a composition having an alcohol represented by the following general formula (3) and a polyblocked isocyanate in the same particles, a reaction product of the alcohol and a polyisocyanate, and a reaction product of the alcohol and a blocking agent capable of reacting with an isocyanate group and a polyisocyanate.

[0082] [Chemical formula]

[0083] [In general formula (3), n 31 n is an integer between 3 and 8. 31 -n 32 n is an integer from 1 to 7, and n 32 is an integer from 1 to 7, and R 31 A is a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms or an acyl group having a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms, and A is at least one selected from the group consisting of a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 6 or less carbon atoms with a 3-6 valency, a residue obtained by removing a hydroxyl group from a dimer or trimer of the said polyhydric alcohol, and a residue obtained by removing a hydroxyl group from an intramolecular dehydrated cyclized product of a polyhydric alcohol with a 5-6 valency.

[0084] In an alcohol represented by general formula (3), R 31 This is a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms or an acyl group having a saturated aliphatic hydrocarbon group having 16 to 32 carbon atoms. Due to the ease of obtaining raw materials, the number of carbon atoms is preferably 16 to 22, and an acyl group is particularly preferred.

[0085] Examples of polyhydric alcohols that become residue A of the alcohol represented by general formula (3) include trihydric alcohols such as 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-ethyl-2-hydroxymethyl-1,3-propanediol (trimethylolpropane), 3-hydroxyethyl-3-methyl-1,5-pentanediol (triethylolethane), and 3-ethyl-3-hydroxyethyl Examples of polyhydric alcohols other than those listed above include trihydric-1,5-pentanediol (triethylolpropane) and tetrahydric alcohol 2,2-bis(hydroxymethyl)-1,3-propanediol (pentaerythritol). Other polyhydric alcohols with a valency of three or higher include sugar alcohols, such as glycerin, erythritol, treitol, arabinitol, xylitol, ribitol, iditol, allitol, galactitol, glucitol (sorbitol), mannitol, talitol, inositol, boremitol, and perseitol. Among these, glycerin, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 3-ethyl-3-hydroxyethyl-1,5-pentanediol, and 2,2-bis(hydroxymethyl)-1,3-propanediol are preferred.

[0086] Examples of dehydrated cyclized polyhydric alcohols that become residue A of the alcohol represented by general formula (3) include 1,4-anhydrosorbitol, 1,5-anhydrosorbitol, and 1,4,3,6-dianhydrosorbitol as dehydrated cyclized products of sorbitol. Among these, 1,4-anhydrosorbitol and 1,5-anhydrosorbitol are preferred.

[0087] Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. Examples of aliphatic polyisocyanates include 1,4-tetramethylene diisocyanate, 1, Examples of polyisocyanates include 5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Examples of alicyclic polyisocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), bis-(4-isocyanatocyclohexyl)methane (hydrogenated MDI), norbornane diisocyanate, etc. Examples of aromatic polyisocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate Examples of suitable polyisocyanates include crude MDI, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylenediisocyanate. Aromatic aliphatic polyisocyanates include, for example, 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, and α,α,α',α'-tetramethylxylylenediisocyanate. It is also preferable to use isocyanate modified products obtained by reactions of these compounds, such as adduct-type polyisocyanates, uretdione reactions, isocyanurate reactions, carbodiimide reactions, uretonimination reactions, biuret reactions, and mixtures thereof.

[0088] As a blocking agent introduced into isocyanate compounds, one active hydrogen atom is added to the molecule. The compounds have the above characteristics and can be used individually or in appropriate combinations of two or more. Examples of blocking agents include alcohol compounds, alkylphenol compounds, phenol compounds, activated methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds, imine compounds, pyrazole compounds, and bisulfites. Among these, acid amide compounds, activated methylene compounds, oxime compounds, and pyrazole compounds are preferred, and ε-caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole can be preferably used.

[0089] (Liquid medium) The fiber surface treatment agent of the present invention may contain other liquid media in addition to water. Examples of liquid media other than water include alcohols, glycols, glycol ethers, glycol esters, halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, organic acids, etc., and aqueous media are preferred in terms of solubility and ease of handling. An aqueous media means water, water-soluble organic solvents, and mixtures thereof. As the water-soluble organic solvent, one or more water-soluble organic solvents selected from the group consisting of water-soluble monoalcohols, water-soluble glycols, water-soluble glycol ethers, and water-soluble glycol esters are preferred.

[0090] (Surfactants) There are no particular limitations on the surfactant used; for example, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymeric surfactants, etc., can be used. These surfactants may be used individually or in combination of two or more types. Using only a cationic surfactant, only a nonionic surfactant, or a combination of a cationic surfactant and a nonionic surfactant is particularly preferable when treating textile products with the aqueous emulsion dispersion. The surfactant is a component that is suitably blended when preparing components A and B.

[0091] Examples of anionic surfactants include various fatty acid salts, alkylbenzene sulfonates, alkanesulfonates, alkyl sulfate esters, alkyl phosphate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene-substituted phenyl ether sulfates, and polycarboxylates. Counterions include, but are not limited to, sodium, potassium, calcium, ammonium, and triethanolamine.

[0092] Examples of nonionic surfactants include nonionic surfactants that do not have a (poly)oxyethylene group and nonionic surfactants that have a (poly)oxyethylene group. Examples of nonionic surfactants that do not have a (poly)oxyethylene group include sorbitan fatty acid esters, fatty acid glycerides, and sucrose fatty acid esters. Examples of nonionic surfactants that have a (poly)oxyethylene group include polyoxyethylene polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxyalkylene alkenyl ethers such as polyoxyethylene alkenyl ethers, polyoxyethylene polyoxypropylene alkenyl ethers, and polyoxyethylene polyoxybutylene alkenyl ethers, as well as polyoxyethylene fatty acid esters, fatty acid alkanolamides, and pluronic surfactants, but are not limited to these.

[0093] Cationic surfactants can include, for example, various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, quaternary salts such as polyoxyethylene alkylamine quaternaries, as well as amine salts obtained by neutralizing amines with a suitable acid, such as alkylamine salts, alkyldimethylamine salts, and polyoxyethylene alkylamine salts. Counterions include, but are not limited to, chloride ions, bromide ions, sulfate ions, formate ions, acetate ions, methyl sulfate ions, and ethyl sulfate ions.

[0094] Examples include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, and acetate betaines. Specifically, examples include, but are not limited to, long-chain amine oxides, lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0095] The proportion of surfactant in the solid content (components other than water) of the fiber surface treatment agent of the present invention is not particularly limited, but is preferably about 2 to 8% by mass.

[0096] (Method for manufacturing surface treatment agents for textiles) In the present invention, the method described in Japanese Patent Application Publication No. 2017-218713 can be used to produce a polymer or emulsion dispersion of hydrophobic compound B1. Furthermore, the method used to produce an emulsion of hydrophobic compound B2 can be a method in which hydrophobic compound B2, a surfactant, and a liquid medium containing at least water are emulsified by the mechanical force of an emulsifier. Hydrophobic compound B3 can be produced by the method described in WO2014 / 160906 or WO2017 / 199726. However, the methods for producing hydrophobic compounds B1, B2, or B3 are not limited to these, and other conventionally known production methods may be used.

[0097] In the production of the polymer of component A in the present invention, the monomer may be polymerized using any of the growth-active species, radical, cation, or anion, as long as the effects of the present invention are produced, but radical polymerization is preferred from a production viewpoint. Furthermore, the monomer may be charged in either a bulk charge method in which the monomer is charged all at once, or a dropwise charge method in which the monomer is added continuously.

[0098] The polymer of component A in this invention can be produced using any of the conventional radical polymerization methods, and the polymerization reaction conditions can also be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. Among these, emulsion polymerization is preferred because it allows the polymerization step and the emulsification and dispersion step of the polymer to be performed in a single step.

[0099] In emulsifying component A in the present invention, it is preferable to use an emulsifier such as an ultrasonic emulsifier / disperser, homomixer, or homogenizer to make the particles of the aqueous emulsion dispersion smaller.

[0100] Furthermore, when preparing component A by emulsion polymerization, a general radical initiator can be used, and components derived from such radical initiators may be included in the fiber surface treatment agent of the present invention. Radical polymerization initiators include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. Specifically, examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis(2-diaminopropane)hydrochloride, and 2,2-azobis(2,4-dimethylvaleronitrile), with water-soluble ones being preferred.

[0101] Chain transfer agents may be used in polymerization. Examples of chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol, as well as inorganic salts such as sodium hypophosphate and sodium bisulfite.

[0102] The emulsion dispersion of component A obtained by emulsion polymerization can be used as is, or, if necessary, subjected to known processing steps such as concentration, extraction, and purification to become an aqueous emulsion dispersion.

[0103] In the aqueous emulsion dispersion constituting the surface treatment agent for textiles of the present invention, component A is present in an amount of 12 to 60% by mass, based on the total mass of component A and component B. From the viewpoint of imparting overall superior properties to textile products in the aforementioned respects, the proportion of component A in the aqueous emulsion dispersion is preferably about 15 to 50% by mass, and more preferably about 20 to 40% by mass.

[0104] Furthermore, in the aqueous emulsion dispersion of the present invention, the average particle size of the dispersion containing component A (dispersed particles containing component A, for example, an aqueous emulsion dispersion of component A, or a composite aqueous emulsion dispersion of component A and component B) is less than 3.0 μm. From the viewpoint of imparting overall superior properties to textile products in the aforementioned respects, the average particle size of the dispersion containing component A is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.5 μm or less.

[0105] In the aqueous emulsion dispersion constituting the surface treatment agent for textiles of the present invention, component B is present in an amount of 88 to 40% by mass, based on the total mass of component A and component B. From the viewpoint of imparting overall superior properties to textile products in the aforementioned respects, the proportion of component B in the aqueous emulsion dispersion is preferably about 50 to 85% by mass, and more preferably about 60 to 80% by mass.

[0106] The total proportion of component A and component B in the solid content (components other than water) of the fiber surface treatment agent of the present invention is not particularly limited, but is preferably 60% by mass or more, and more preferably 70% by mass or more.

[0107] In the fiber surface treatment agent of the present invention, the forms of components A and B in the aqueous emulsion dispersion are not particularly limited. For example, the aqueous emulsion dispersion may contain particles in which components A and B are present in the same particle. In this form, components A and B are contained in the same particle and exist in the aqueous emulsion dispersion in this state.

[0108] Furthermore, the aqueous emulsion dispersion may contain particles composed of component A and particles composed of component B. In this form, component A and component B are contained in separate particles, and two types of particles are present in the aqueous emulsion dispersion.

[0109] The surface treatment agent for fibers of the present invention can be suitably obtained, for example, by mixing an aqueous emulsion dispersion of component A and an aqueous emulsion dispersion of component B. By obtaining the surface treatment agent for fibers of the present invention in this manner, a surface treatment agent for fibers consisting of an aqueous emulsion dispersion containing particles composed of component A and particles composed of component B can be suitably obtained.

[0110] Furthermore, the fiber surface treatment agent of the present invention can also be suitably obtained by preparing an aqueous emulsion dispersion of either component A or component B, and polymerizing the monomer constituting the other component in the aqueous emulsion dispersion. By obtaining the fiber surface treatment agent of the present invention in this way, a fiber surface treatment agent consisting of an aqueous emulsion dispersion containing particles in which component A and component B exist in the same particle can be suitably obtained. As a specific example of this method, an aqueous emulsion dispersion of component B is prepared, and component A is prepared in the aqueous emulsion dispersion of component B to obtain particles in which component A is coated around the particles of component B. Alternatively, an aqueous emulsion dispersion of component A may be prepared, and component B may be prepared in the aqueous emulsion dispersion of component A to obtain particles in which component B is coated around the particles of component A.

[0111] (Additives) Furthermore, the surface treatment agent for fibers of the present invention may contain any additives insofar as they produce the effects of the present invention. Examples of additives include textile agents such as surfactants, crosslinking agents, inorganic anti-slip agents, softeners, SR agents, wrinkle inhibitors, flame retardants, antistatic agents, and heat-resistant agents, as well as antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents. These additives can be used individually or in appropriate combinations of two or more.

[0112] The textile surface treatment agent of the present invention may contain paraffin wax, silicone wax, methyl hydrogen silicone, octadecylethylene urea, alkyl ketene dimer, zirconyl octoate, etc., to improve water repellency and adjust texture. The amount of the above compounds used is 0.01 to 50% by mass, preferably 0.01 to 40% by mass, and more preferably 0.01 to 30% by mass, relative to the solid content (components other than water) of the textile surface treatment agent of the present invention.

[0113] Furthermore, when applying the fiber surface treatment agent of the present invention to textile products, it is preferable to use in combination an aqueous emulsion of a bifunctional or more blocked isocyanate, a crosslinking agent such as N-methylolmelamine, etc.

[0114] Bifurcation polyisocyanates with two or more functions can be obtained by known methods by reacting a bifunctional or more isocyanate with a suitable blocking agent. Examples of isocyanates include 4,4'-bisisocyanatophenylmethane, toluene diisocyanate, hexamethylene diisocyanate, trimers of diisocyanates, and trimethylolpropane adducts.

[0115] Furthermore, examples of isocyanate blocking agents include secondary or tertiary alcohols, active methylene compounds, phenols, oximes, substituted pyrazoles, and caprolactams. Typically, these blocked isocyanates are used after being emulsified or dispersed using surfactants by known methods. Alternatively, by first blocking 70-95% of the total isocyanate groups and then reacting the remaining isocyanate groups with polyalkylene glycols of an appropriate molecular weight, particularly polyethylene glycol, the blocked isocyanates exhibit self-emulsifying properties, which not only improves the wash durability of textile surface treatment agents but also enhances product stability.

[0116] Examples of N-methylolmelamine include trimethylolmelamine and hexamethylolmelamine.

[0117] The proportion of the crosslinking agent in the solid content (components other than water) of the fiber surface treatment agent of the present invention is not particularly limited, but is preferably about 1 to 20% by mass.

[0118] Furthermore, known inorganic anti-slip agents that are incorporated into surface treatment agents for textiles can be used, such as colloidal silica and hydrophobic silica.

[0119] The proportion of the inorganic anti-slip agent in the solid content (components other than water) of the fiber surface treatment agent of the present invention is not particularly limited, but is preferably about 1 to 15% by mass.

[0120] (Preparation of processing solution for fiber surface treatment agent) The textile surface treatment agent of the present invention may be used as a stock solution diluted with water when applied to textile products, or it may be used at its original concentration when applied to textile products. When used as a stock solution, the solid content (components other than water) contained in the textile surface treatment agent of the present invention is approximately 15 to 50% by mass. When preparing a processing solution by diluting the textile surface treatment agent of the present invention with water, various agents as described above, such as crosslinking agents, may be optionally added in addition to water. The solid content (components other than water) contained in the processing solution of the textile surface treatment agent of the present invention used when applied to textile products is approximately 0.4 to 3.0% by mass.

[0121] (Fiber processing) The fiber surface treatment agent of the present invention can be used to treat fabrics in known ways. Examples of treatment methods include continuous methods and batch methods. In the continuous method, first, a processing solution is prepared by using the fiber surface treatment agent as is or by diluting it with water. When preparing the processing solution, it is also preferable to optionally add the various chemicals mentioned above, such as crosslinking agents, in addition to water. Next, the workpiece (i.e., the textile product) is continuously fed into an impregnation device filled with the processing solution, and after impregnating the workpiece with the processing solution, the excess processing solution is removed. The impregnation device is not particularly limited, and padders, kissroll type impregnation devices, gravure coater type impregnation devices, spray type impregnation devices, foam type impregnation devices, coating type impregnation devices, etc., can be preferably used, with padder type being particularly preferred. Subsequently, a dryer is used to remove any remaining water from the workpiece. The dryer is not particularly limited, but spread dryers such as hot flools and tenters are preferred. The continuous method is preferably used when the workpiece is a fabric such as a woven fabric. The batch method consists of a step of immersing the workpiece in a processing solution and a step of removing any remaining water from the treated workpiece. The batch method is preferably used when the workpiece is not in the form of fabric, for example, loose hair, top, sliver, hank, tow, yarn, etc., or when it is not suitable for continuous methods such as knitted fabrics. For the immersion step, for example, a cotton dyeing machine, cheese dyeing machine, liquid flow dyeing machine, industrial washing machine, beam dyeing machine, etc. can be used. For the water removal operation, a cheese dryer, beam dryer, hot air dryer such as a tumble dryer, high-frequency dryer, etc. It is preferable to perform a dry heat treatment on the workpiece to which the fiber surface treatment agent of the present invention has been applied. The temperature for the dry heat treatment is preferably 120 to 180°C, and particularly preferably 160 to 180°C. The time for the dry heat treatment is preferably 10 seconds to 3 minutes, and particularly preferably 1 to 2 minutes. There are no particular limitations on the method of dry heat treatment, but a tenter is preferred when the workpiece is in the form of fabric.

[0122] The textile surface treatment agent of the present invention broadly imparts water repellency and wash durability to natural fibers such as cotton, silk, linen, and wool, as well as synthetic fibers such as polyester, nylon, acrylic, and spandex, and textile products using these materials. Furthermore, there are no restrictions on its form or shape; it is not limited to raw material forms such as staples, filaments, tow, and yarn, but can also be treated with the textile surface treatment agent composition of the present invention in a variety of processed forms such as woven fabrics, knitted fabrics, stuffing, nonwoven fabrics, paper, sheets, and films.

[0123] The textile product of the present invention is obtained by treating the surface of the aforementioned type of fiber by the method described above. Details of the surface treatment agent for fibers of the present invention are as described above. [Examples]

[0124] The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

[0125] [Synthesis Example 1] In a 300 mL flask, 80 g of styrene, 0.4 g of sanizol C, 2.45 g of polyoxyethylene (9 mol) oleyl ether, 2.45 g of polyoxyethylene (13 mol) oleyl ether, and 200 g of deionized water were placed and emulsified by high-speed stirring at 60°C to obtain a mixture. Subsequently, the mixture was treated with a high-pressure homogenizer at 40 MPa while maintaining the temperature at 40°C to obtain an emulsion. The emulsion was transferred to a 300 mL three-necked flask fitted with a reflux condenser, cooled to room temperature, and then 0.3 g of azobis(isobutylamidine) dihydrochloride was added. A radical polymerization reaction was carried out at 70°C for 15 hours under a nitrogen atmosphere. Subsequently, the emulsion dispersion was diluted with deionized water to a component concentration of 20% by mass to obtain an emulsion dispersion of component A. The composition is shown in Table 1.

[0126] [Synthesis Examples 2-10, Comparative Synthesis Examples 1-2] Except for changing the monomer composition as shown in Table 1, emulsified dispersions of each component A were obtained in the same manner as in Synthesis Example 1. The compositions are shown in Table 1.

[0127] [Synthesis Example 11] Based on the method described in Japanese Patent Application Publication No. 2017-218713, an emulsion dispersion B1-1 (an aqueous emulsion dispersion with a concentration of 20% by mass of component B) was obtained by emulsifying and dispersing hydrophobic compound B1, a polymer containing 98% by mass of stearyl acrylate and 2% by mass of hydroxyethyl methacrylate, with a cationic surfactant and a nonionic surfactant.

[0128] [Synthesis Example 12] Based on the method described in Japanese Patent Application Publication No. 2017-218713, an emulsion dispersion B1-2 (an aqueous emulsion dispersion with a concentration of 20% by mass of component B) was obtained by emulsifying and dispersing hydrophobic compound B1, a polymer containing 92% by mass of stearyl acrylate, 3% by mass of one-terminated methacrylic modified silicone with a functional group equivalent of 900, 3% by mass of one-terminated methacrylic modified silicone with a functional group equivalent of 12000, and 2% by mass of hydroxyethyl methacrylate, with a cationic surfactant and a nonionic surfactant.

[0129] [Synthesis Example 13] 200 g of the emulsion dispersion B1-2 was placed in a 300 mL flask. Next, a mixture of 17.2 g of styrene and 20 g of tripropylene glycol was added dropwise over 45 minutes, and 0.3 g of azobis(isobutylamidine) dihydrochloride was added. A radical polymerization reaction was carried out at 70°C for 15 hours under a nitrogen atmosphere. After that, the emulsion dispersion was diluted with deionized water to a polymer concentration of 20% by mass, and an emulsion dispersion of a composite of component A and component B with an average particle size of 0.16 μm was obtained.

[0130] [Synthesis Example 14] 200 g of the emulsion dispersion B1-2 was placed in a 300 mL flask. Next, a mixture of 17.2 g of methyl methacrylate, 0.53 g of polyoxyethylene (9 mol) oleyl ether, and 0.53 g of polyoxyethylene (13 mol) oleyl ether was added dropwise over 45 minutes. Then, 0.3 g of azobis(isobutylamidine) dihydrochloride was added, and a radical polymerization reaction was carried out at 70°C for 15 hours under a nitrogen atmosphere. After that, the emulsion dispersion was diluted with deionized water to a polymer concentration of 20% by mass, and an emulsion dispersion of a composite of component A and component B with an average particle size of 0.16 μm was obtained.

[0131] <Glass transition temperature of homopolymers> For the glass transition temperatures (Tg) of the homopolymers of each monomer, the values ​​listed in the Polymer Handbook (Third Edition, published in 1990 by John Wiley & Sons) were used for styrene, isobornyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, hydroxyethyl methacrylate, and 2-ethylhexyl methacrylate. For polyoxyalkylene alkenyl ethers and stearyl acrylates, the Tg was measured by differential scanning calorimeter (DSC) after solution polymerization and thorough drying of the polymers. The glass transition temperatures of the homopolymers are shown in Table 1.

[0132] <Particle size of emulsion dispersion> The average particle size of each emulsion dispersion was measured using a laser diffraction / scattering particle size distribution analyzer LA-300 (manufactured by Horiba, Ltd.), and the arithmetic mean diameter (D50) was used. The results are shown in Table 1.

[0133] [Table 1]

[0134] [Examples 1-16] 、22~25 Comparative Example 1~ 8 ] The emulsified dispersion B1-1 , or B1-2The emulsified dispersions of each component A synthesized above, along with Meikanate FM-1 (blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd.: 30% active ingredient) as a blocked isocyanate crosslinking agent, and commercially available colloidal silica (Snowtex AK (number mean primary particle size 10-15 nm, M value 0), manufactured by Nissan Chemical Industries, Ltd., "Snowtex" is a registered trademark of the company) as an inorganic anti-slip agent, were blended as shown in Tables 2-4 to create a surface treatment agent for textiles. The composition is shown in Tables 2-4.

[0135] [Example 17] The emulsion dispersion of Synthesis Example 13 (an emulsion dispersion of a composite of component A and component B) and Meikanate FM-1 (blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd.: 30% active ingredient) as a blocked isocyanate crosslinking agent were blended as shown in Table 3 to create a surface treatment agent for textiles. The composition is shown in Table 3.

[0136] [Example 18] The emulsion dispersion of Synthesis Example 14 (an emulsion dispersion of a composite of component A and component B) and Meikanate FM-1 (blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd.: 30% active ingredient) as a blocked isocyanate crosslinking agent were blended as shown in Table 3 to create a surface treatment agent for textiles. The composition is shown in Table 3.

[0137] [Examples 19-20, Comparative Examples 13-14] A hydrophobic compound B2 is used as part of a side-chain diamine-modified silicone (functional group equivalent 11000) containing dimethylsiloxane units at a concentration of 75% or more of the total polymer mass. This side-chain diamine-modified silicone is emulsified and dispersed with a cationic surfactant and a nonionic surfactant. This emulsion dispersion B2-1 (an aqueous emulsion dispersion with a component B concentration of 20% by mass) is then combined with the emulsion dispersions of each component A synthesized above, along with Meikanate FM-1 (blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd.: 30% active ingredient) as a blocked isocyanate crosslinking agent, and commercially available colloidal silica (Snowtex AK (number mean primary particle size 10-15 nm, M value 0), manufactured by Nissan Chemical Industries, Ltd., "Snowtex" is a trademark of the company) as an inorganic anti-slip agent. These components are blended as shown in Table 5 to create a surface treatment agent for textiles. The composition is shown in Table 5.

[0138] [Example 21, Comparative Examples 15-17] Based on Publication No. WO2014 / 160906, the hydrophobic compound B2, obtained by condensing sorbitan tristearate and hexamethylene diisocyanate biuret in a weight ratio of hydroxyl group equivalents to isocyanate equivalents, is emulsified and dispersed with a cationic surfactant and a nonionic surfactant to form emulsion dispersion B3-1 (an aqueous emulsion dispersion with a concentration of component B of 25% by mass), the emulsion dispersions of each component A synthesized above, Meikanate FM-1 (blocked isocyanate manufactured by Meisei Chemical Industry Co., Ltd.: 30% active ingredient) as a blocked isocyanate crosslinking agent, and commercially available colloidal silica (Snowtex AK (number average primary particle size)) as an inorganic anti-slip agent. A surface treatment agent for textiles was prepared by blending 10-15 nm (M value 0), manufactured by Nissan Chemical Industries, Ltd. ("Snowtex" is a trademark of the company), as shown in Table 6. The composition is shown in Table 6.

[0139] <Evaluation of antipolymer tackiness> Approximately 1g of each fiber surface treatment agent obtained above was placed in an aluminum cup and dried in a 110°C dryer for 1 hour. After drying, the temperature was lowered to 40°C, and the formed film was touched with an index finger to evaluate its tackiness and how well it adhered to the finger. ○ indicated no tackiness and no film adhering to the finger, △ indicated slight tackiness but no film adhering to the finger, and × indicated tackiness and a film adhering to the finger.

[0140] <Evaluation of water repellency> Each surface treatment agent for fibers obtained above was padded onto polyester taffeta fabric (fiber diameter 56 dtex) and nylon high-density taffeta fabric (fiber diameter 44 dtex). The fabric was then nipped (30% and 42% pickup) using two rubber rollers, dried at 110°C for 2 minutes, and cured at 170°C for 1 minute to prepare evaluation fabrics. The water repellency of the obtained evaluation fabrics was evaluated using the spray method of JIS L 1092 (2009). In all cases, the evaluation fabrics were washed and air-dried. The water repellency is expressed as a 5-level numerical value from 1 to 5 (JIS default value) as shown in Tables 2 to 6, and a + (-) sign next to the number indicates that it is slightly better (worse) than the numerical evaluation value. The results are shown in Tables 2 to 6.

[0141] (Evaluation of water-repellent properties and their wash durability) The evaluation fabric prepared as described above was subjected to 0 washes (HL-0(N)), then 10 washes (HL-10(N)) and 20 washes (HL-20(N)) according to the washing method described in JIS L 1092 (2009), and the water repellency of the evaluation fabric was evaluated in the same manner. The results are shown in Tables 2 to 6.

[0142] <Evaluation of seam slippage> Using the surface treatment agents for each fiber obtained above, polyester taffeta fabric was treated in the same manner as for water repellency evaluation. A warp thread slippage test was performed at a load of 117.2 N (12 kgw) according to JIS L 1096-99.8.21.1 Method B, and the seam slippage (mm) was measured. The results are shown in Tables 2 to 6.

[0143] Tables 2 to 6 show the seam slippage evaluation. A rating of ◎ fully meets the apparel performance requirements. A rating of ○ meets the apparel performance requirements with less stringent standards, or may be able to achieve a seam length of less than 3.0 mm with other test fabrics. Ratings ○ to △ are somewhere between a rating of ○ and a rating of △, and either meet the apparel performance requirements with less stringent standards, or may be able to achieve a seam length of less than 3.0 mm with other test fabrics. A rating of △ shows a clear improvement in seam slippage compared to polymer B alone. A rating of × does not meet the apparel performance requirements.

[0144] <Evaluation of water pressure resistance> Using the surface treatment agents for fibers obtained in Examples 2 and 11 and Comparative Examples 2 and 6, polyester woolly cloth was treated in the same manner as in the water repellency evaluation. Then, evaluation cloths were prepared by calendering using a metal roll-resin roll calendering unit at 150°C and a nip pressure of 130 kg / cm. Using the obtained evaluation cloths, water pressure resistance was tested according to Method A of the hydrostatic pressure method described in JIS L 1096 (2009), and the average of 5 measurements was rounded to the nearest 1 cm. The results are shown in Tables 2 and 4.

[0145] [Table 2]

[0146] [Table 3]

[0147] [Table 4]

[0148] [Table 5]

[0149] [Table 6]

[0150] Based on the above evaluations, Examples 1-9, 11, and 13-18 all show good performance in terms of water repellency (HL-0), wash durability, and seam slippage, and have an excellent balance of performance, resulting in a high overall rating. Examples 10 and 12 have slightly inferior wash durability for Ny, but excel in the important initial water repellency (NL-0), and also exhibit minimal seam slippage, resulting in overall good performance. Examples 19 and 20 exhibit significant seam slippage, but have particularly excellent water repellency and wash durability, resulting in a high overall rating. Example 21 shows a decrease in 20-wash durability (NL-20), but excels in the important initial water repellency (NL-0) for textile surface treatment agents, and also exhibits minimal seam slippage, resulting in overall good performance and a high overall rating. In addition to the above, Examples 2 and 11 have high water pressure resistance values, which is excellent.

[0151] In contrast to this, Comparative Examples 1-6, Example 23 Although the water repellency (HL-0) is good, the seam slippage is significant, therefore the overall evaluation is as follows: 19, 20 Inferior. Comparative Example 7 has a poor water-repellent wash durability (HL-10) for both PET and Ny, resulting in a low overall evaluation. Comparative Example 8, Example 22 Although the water repellency (HL-0) of PET is good, the water repellency (HL-0) of Ny is somewhat low, and the wash durability of the water repellency is poor, so the overall rating is low. Example 24 , 25 Although seam slippage was minimal, the water repellency was extremely low, and therefore it could not impart excellent water repellency to textile products, resulting in a low overall evaluation. Comparative Example 13 had good water repellency (HL-0), but seam slippage was too great, resulting in a low overall evaluation. Comparative Example 14 had poor water repellency and wash durability, resulting in a low overall evaluation. Comparative Example 15 had good water repellency (HL-0), but its wash durability was somewhat low and seam slippage was significant, resulting in a low overall evaluation. Comparative Examples 16 and 17 had extremely low wash durability, resulting in a low overall evaluation. In addition to the above, Comparative Examples 2 and 6 had lower water pressure resistance values ​​than the Examples.

Claims

1. A dispersion used to improve seam slippage in a surface treatment agent for textiles that does not contain fluorine atoms, and which contains component A, A dispersion comprising a polymer in which component A is at least one ethylenically unsaturated monomer a represented by the following general formula (4), and at least one monomer having a glass transition temperature of 50°C or higher is present in a repeating unit in an amount exceeding 55% by mass, and the average particle size is less than 3.0 μm. 【Chemistry 1】 [In general formula (4), R 41 is a hydrogen atom, a methyl group, or a chloro group, and n 41 is an integer of 0 or 1. When n 41 is 0, R 42 is a cyclic hydrocarbon group having less than 16 carbon atoms that may have one or more chloro groups, bromo groups, or chloromethyl groups. When n 41 is 1 and R 41 is a methyl group or a chloro group, R 42 is a cyclic hydrocarbon group having less than 16 carbon atoms that may have one or more chloro groups, bromo groups, or chloromethyl groups, a phenyl group or benzyl group that may have one or more chloro groups or bromo groups, or a saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. When n 41 is 1 and R 41 is a hydrogen atom, R 42 is a cyclic hydrocarbon group having less than 16 carbon atoms that may have one or more chloro groups, bromo groups, or chloromethyl groups.]

2. The dispersion according to claim 1, wherein in component A, monomer a is at least one selected from the group consisting of a1 monoethylene unsaturated monomer having a styrene skeleton represented by the following general formula (5), a2 monoethylene unsaturated monomer having a cyclic aliphatic skeleton represented by the following general formula (6), and a3 other monoethylene unsaturated monomer represented by the following general formula (7). 【Chemistry 2】 [In general formula (5), R 51 R is a hydrogen atom, a methyl group, or a chloro group. 52 and R 53 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a chloro group, or a chloromethyl group. 【Transformation 3】 [In general formula (6), R 54 R is a hydrogen atom, a methyl group, or a chloro group. 55 This is a cyclic aliphatic group having less than 16 carbon atoms, which may have one or more chloro, bromo, or chloromethyl groups. 【Chemistry 4】 [In general formula (7), R 56 R is a methyl group or a chloro group, 57 This is a methyl group, an ethyl group, or a tert-butyl group.

3. The dispersion according to claim 1 or 2, wherein the monomer constituting the polymer of component A further comprises a crosslinkable ethylenically unsaturated monomer d having at least one selected from the group consisting of a hydroxyl group, an epoxy group, an acetoacetyl group, a carbonyl group, a chloromethyl group, an amide group, an N-alkoxymethylamide group, a blocked isocyanate group, an oxazoline group, a carboxyl group, a sulfonic acid group, and an alkoxysilyl group.

4. A dispersion according to any one of claims 1 to 3, comprising a crosslinking agent in addition to component A.

Images