Dispersion

Abstract

To provide: a dispersion with which it is possible to achieve excellent processing stability of an organo-modified silicone and excellent water wicking resistance (anti-wicking property) and hue of a fiber product; a fiber product treated with the dispersion liquid; and a method for producing the fiber product. In one embodiment, provided is a dispersion containing an organo-modified silicone (alpha) having a specific structure, wherein the amount of cyclic siloxane (gamma) having a specific structure in the dispersion is 1000 mass ppm or less. In one embodiment, the dispersion further includes a hydrophobic polymer (beta) having a specific structure.

Description

[Technical Field]

[0001] The present invention relates to a dispersion and a textile product treated with the dispersion. [Background technology]

[0002] Conventionally, water-repellent additives and water-repellent compositions containing organo-modified silicones and hydrophobic polymers are known for imparting water repellency to textile products and the like. Patent Document 1 describes a water-repellent additive for non-fluorine water-repellent agents, which includes an organo-modified silicone of a specific structure. Patent Document 2 describes a surface treatment agent comprising (A) a water-repellent and oil-repellent polymer having repeating units derived from at least one water-repellent and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having hydrocarbon groups with 7 to 40 carbon atoms, in an amount of 30 to 100% by weight relative to the water-repellent and oil-repellent polymer, (B) a silicone polymer of a specific structure, and (C) a liquid medium. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2017 / 150176 [Patent Document 2] International Publication No. 2019 / 163570 [Overview of the project] [Problems that the invention aims to solve]

[0004] The technology described in Patent Document 1 aims to obtain a water-repellent additive that can improve the durable water repellency of non-fluorine-based water repellents, and the technology described in Patent Document 2 aims to obtain a surface treatment agent that is excellent in water-repellent, oil-repellent, and slip-resistant properties. However, these technologies lacked sufficient processing stability of the organo-modified silicone in the treatment agent, water absorption resistance (anti-wicking) of the textile products treated with the treatment agent, and hue.

[0005] The present invention aims to solve the above problems and provide a dispersion liquid capable of realizing excellent processing stability of organo-modified silicone, good water absorption resistance (anti-wicking property) of fiber products, and hue, a fiber product treated with the dispersion liquid, and a method for producing the fiber product.

Means for Solving the Problems

[0006] The present disclosure includes the following items. [Item 1] The following general formula (1):

Chemical formula

[0007] According to one aspect of the present invention, a dispersion, a textile product treated with the dispersion, and a method for producing the textile product can be provided, which can achieve excellent processing stability of organo-modified silicone, good water absorption resistance (anti-wicking properties) and hue of the textile product. [Modes for carrying out the invention]

[0008] Preferred embodiments of the present invention (hereinafter also referred to as "this embodiment") will be described in detail below. However, the present invention is not limited to the following embodiments.

[0009] ≪Dispersion liquid≫ One aspect of the present invention is the following general formula (1): [ka] [In formula (1), R 20 , R 21 and R 22 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms. R 23 This represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms. R 30 , R 31 , R 32 , R 33 , R 34 and R 35 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms, and, a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, (a+b) is between 10 and 200, and if a is greater than or equal to 2, there are multiple R values. 20 and R21 These can be the same or different, and if b is 2 or more, there can be multiple R 22 and R 23 These may be the same or different. A dispersion containing organo-modified silicone (α) represented by, The following general formula (1a) is present in the dispersion: [ka] [In formula (1a), R 20 and R 21 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a1 is an integer less than or equal to 30. The present invention provides a dispersion in which the amount of cyclic siloxane (γ) represented by is 1000 ppm by mass or less.

[0010] <Cyclic Siloxane (γ)> The cyclic siloxane (γ) present in the dispersion is typically a by-product generated during the synthesis of hydrogen silicone, which is a raw material for organo-modified silicone (α). Due to its structure represented by general formula (1a), cyclic siloxane (γ) tends to have a lower melting point and lower water repellency compared to organo-modified silicone (α). Our studies have shown that when a large amount of such cyclic siloxane (γ) is present in a dispersion containing organo-modified silicone (α), it can lead to: (1) deterioration of processing stability, such as the adhesion of a gum-like substance (gum-up) to equipment used when processing a substrate with the dispersion (for example, a mangle used when squeezing a substrate treated with the dispersion to produce a textile product); (2) insufficient water absorption resistance (anti-wicking properties) of the textile product treated with the dispersion; and / or (3) poor coloration of the textile product treated with the dispersion. Therefore, it is considered advantageous to have a small amount of cyclic siloxane (γ) in the dispersion. On the other hand, from the viewpoint of the availability of organo-modified silicone (α), it is advantageous to allow the presence of cyclic siloxane (γ) as a by-product during the synthesis of the organo-modified silicone (α). Further investigation by the inventors revealed that when the amount of cyclic siloxane (γ) in the dispersion is below a predetermined level, the processing stability of the dispersion, the water absorption resistance (anti-wicking properties) of the textile product, and the hue of the textile product are improved while maintaining the availability of organo-modified silicone (α).

[0011] In formula (1a), R 20 and R 21 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms.

[0012] In formula (1a), a1 is an integer less than or equal to 30. In one embodiment, a1 is 3 or greater. On the other hand, when a1 is less than or equal to a predetermined value, the adverse effect on the product stability of the dispersion tends to be reduced. From this viewpoint, a1 is preferably 30 or less, or 20 or less, or 10 or less.

[0013] The concentration of cyclic siloxane (γ) in the dispersion is, in one embodiment, 1000 ppm by mass or less, preferably 500 ppm by mass or less, or 100 ppm by mass or less, or 10 ppm by mass or less, or 0 ppm by mass, from the viewpoint of anti-wicking properties, hue of the textile product, and processing stability (gum-up properties). The amount of cyclic siloxane (γ) can be confirmed using GC / MS (gas chromatograph-mass spectrometer).

[0014] Methods for achieving the above-mentioned concentration of cyclic siloxane (γ) in the dispersion include performing processes such as heating, reduced pressure, and distillation during the synthesis of hydrogen silicone, which is a raw material for organo-modified silicone (α).

[0015] <Organo-modified silicone (α)> Organo-modified silicone (α) is given by the following general formula (1): [ka] [In formula (1), R 20 , R 21 and R 22 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms. R 23 This represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms. R 30 , R 31 , R 32 , R 33 , R 34 and R 35 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms, and, a represents an integer greater than or equal to 0, b represents an integer greater than or equal to 1, (a+b) is between 10 and 200, and if a is greater than or equal to 2, there are multiple R values. 20 and R 21 These can be the same or different, and if b is 2 or more, there can be multiple R 22and R 23 These may be the same or different. It is represented by the following. In general formula (1), each constituent unit may be a block, random, or alternating arrangement.

[0016] In general formula (1), the number of carbon atoms in the hydrocarbon group having an aromatic ring with 6 to 50 carbon atoms, or the alkyl group having 6 to 100 carbon atoms, is preferably 6 to 50, 16 to 44, 18 to 42, or 20 to 40, from the viewpoint of initial water repellency and durable water repellency. From the viewpoint of chalk markability, the preferred values ​​are 6-50, 8-40, 8-36, or 8-24.

[0017] In general formula (1), the alkoxy group having 1 to 4 carbon atoms may be linear or branched. More specifically, the alkoxy group having 1 to 4 carbon atoms is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0018] In general formula (1), the hydrocarbon group having an aromatic ring and having 6 to 50 carbon atoms is, for example, an aralkyl group having 6 to 50 carbon atoms, as shown in general formula (2): [ka] [In formula (2), R 40 This represents an alkylene group with 2 to 6 carbon atoms. R 41 This represents a single bond or an alkylene group having 1 to 4 carbon atoms, and, c represents an integer from 0 to 3, and if c is 2 or 3, there are multiple R 41 They may be the same or different. A base represented by the following general formula (3): [ka] [In formula (3), R 42 This represents an alkylene group with 2 to 6 carbon atoms. R 43This represents a single bond or an alkylene group having 1 to 4 carbon atoms, and, d represents an integer from 0 to 3, and if d is 2 or 3, there are multiple R 43 They may be the same or different. Examples of groups represented by the following are given. The alkylene groups in general formulas (2) and (3) may be linear or branched.

[0019] Examples of the above-mentioned aralkyl groups having 6 to 50 carbon atoms include phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, and naphthylethyl group. Among these, phenylethyl group and phenylpropyl group are preferred because they are easy to manufacture industrially and readily available.

[0020] In the group represented by the above general formula (2), R is easy to manufacture industrially and readily available. 40 The group is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0021] In the group represented by the above general formula (3), R is easy to manufacture industrially and readily available. 42 d is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0022] As the above-mentioned hydrocarbon group having an aromatic ring and having 6 to 50 carbon atoms, the above-mentioned aralkyl group having 6 to 50 carbon atoms and the group represented by the above-mentioned general formula (2) are preferred in that they are easy to manufacture industrially and readily available, and the above-mentioned aralkyl group having 6 to 50 carbon atoms is more preferred in that it can improve the water repellency of the resulting textile product.

[0023] The above C6-C100 alkyl groups may be linear or branched. Examples of C6-C100 alkyl groups include octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, 1-hexacocenyl (C26), 1-octacocenyl (C28), 1-triacontenyl (C30), and 1-dotriacontenyl (C32).

[0024] In terms of being easy to manufacture industrially and readily available, R in general formula (1) 20 , R 21 and R 22 Each of these is preferably independently a hydrogen atom or a methyl group, and more preferably a methyl group.

[0025] From the viewpoint of initial water repellency and durable water repellency, in general formula (1), R 23 It is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, more preferably 16 to 44, or 18 to 42, or 20 to 40 carbon atoms, and from the viewpoint of chalk markability, in general formula (1), R 23 It is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, and more preferably 8 to 40, 8 to 36, or 8 to 24 carbon atoms.

[0026] In general formula (1), a is an integer greater than or equal to 0. a is preferably 40 or less, and more preferably 30 or less, in terms of ease of industrial manufacture, availability, and superior peel strength of the resulting textile product against resin coating.

[0027] In general formula (1), (a+b) is between 10 and 200. Preferably, (a+b) is between 20 and 100, and more preferably between 40 and 60, in terms of ease of industrial manufacture and availability. When (a+b) falls within the above range, the manufacturing and handling of the silicone itself tends to be easier.

[0028] The organo-modified silicone (α) of this embodiment can be synthesized by conventionally known methods. For example, the organo-modified silicone (α) of this embodiment can be obtained by hydrosilylation of a silicone having a SiH group with an aromatic compound having a vinyl group and / or an α-olefin.

[0029] Examples of silicones having the SiH group mentioned above include methyl hydrogen silicone with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen siloxane. Among these, copolymers of dimethylsiloxane and methyl hydrogen siloxane are preferred from the viewpoint of water repellency.

[0030] The above aromatic compounds having a vinyl group are R in the above general formula (1). 23 In this context, it refers to compounds from which hydrocarbon groups having 6 to 50 carbon atoms and possessing an aromatic ring are derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0031] The above α-olefin is R in the above general formula (1). 23 In this context, it is a compound from which alkyl groups having 6 to 100 carbon atoms are derived. Examples of α-olefins include 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacocene (C28), 1-triaconthene (C30), and 1-dotriaconthene (C32), all of which have 6 to 100 carbon atoms.

[0032] The above hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having the SiH group with the above-mentioned aromatic compound having the vinyl group and the above-mentioned α-olefin in a stepwise or all-at-a-time manner, in the presence of a catalyst as needed.

[0033] The amounts used in the hydrosilylation reaction of the silicone having SiH groups, the aromatic compound having vinyl groups, and the α-olefin can be appropriately selected depending on the SiH group equivalent of the silicone having SiH groups, or the number-average molecular weight, etc.

[0034] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0035] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.

[0036] Furthermore, the hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction will proceed even without a solvent, but a solvent may be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0037] <Dispersion aid> In one embodiment, the dispersion may further contain a dispersion aid. From the viewpoint of ensuring that the organo-modified silicone (α) is present in a good dispersed state (emulsified state in one embodiment) in the dispersion, one or more nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants may be used as the dispersion aid (emulsifying aid in one embodiment). The content of the dispersion aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of organo-modified silicone (α). When the content of the dispersion aid is 0.5 parts by mass or more, the dispersion stability of the organo-modified silicone (α) in the dispersion tends to improve further, and when it is 50 parts by mass or less, the water repellency of the textile product treated with the dispersion tends to improve further.

[0038] Furthermore, a dispersion aid may be used when polymerizing or dispersing (emulsifying in one embodiment) the hydrophobic polymer (β) described later. The dispersion aid used may be the same as that used when dispersing (emulsifying in one embodiment) the organo-modified silicone (α). The content of the dispersion aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, per 100 parts by mass of the hydrophobic polymer (β). When the content of the dispersion aid is 0.5 parts by mass or more, the dispersion stability of the hydrophobic polymer (β) in the dispersion tends to be further improved, and when it is 50 parts by mass or less, the water repellency of the textile product treated with the dispersion tends to be further improved.

[0039] (cationic surfactant) Examples of the cationic surfactant include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, dialkylamine acetates having 8 to 24 carbon atoms, alkylimidazoline quaternary salts having 8 to 24 carbon atoms, and the like. Among these, from the viewpoints of dispersibility (in one aspect, emulsifying property) and processing stability, monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred. Preferable examples of the cationic surfactant include stearyltrimethylammonium sulfate, stearyltrimethylammonium chloride, and the like.

[0040] These cationic surfactants may be used alone or in combination of two or more.

[0041] (Nonionic surfactant) Examples of the nonionic surfactant include alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, polypropylene glycol, and their alkylene oxide adducts, and the like.

[0042] Examples of the alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and the following general formula (AL-1):

Chemical formula

[0043] Examples of polycyclic phenols include monovalent phenols such as phenols and naphthols which may have hydrocarbon groups with 1 to 12 carbon atoms, or their styrene adducts (e.g., styrene, α-methylstyrene, or vinyltoluene), or their benzyl chloride reaction products. Examples of amines include linear or branched aliphatic amines with 8 to 44 carbon atoms.

[0044] Examples of amides include straight-chain or branched fatty acid amides with 8 to 44 carbon atoms.

[0045] Examples of fatty acids include straight-chain or branched fatty acids with 8 to 24 carbon atoms.

[0046] Examples of polyhydric alcohol fatty acid esters include condensation reaction products of polyhydric alcohols and carboxylic acids having 2 to 30 carbon atoms (including the carbon atoms of the carboxyl group). Examples of such polyhydric alcohol fatty acid esters include sorbitan esters, which are composed of sorbitan (alcohol) and carboxylic acids having 2 to 30 carbon atoms (including the carbon atoms of the carboxyl group).

[0047] The carboxylic acid constituting the sorbitan ester has 2 to 30 carbon atoms, preferably 5 to 21. The sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, or a tricarboxylic acid ester of sorbitol and three carboxylic acids, and a monocarboxylic acid ester is preferred.

[0048] Sorbitan esters are given by the following general formula (4): [ka] [In formula (4), R 61represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, R 64 , R 65 and R 66 each independently represents a hydrogen atom, -CO-R 61 , or -(CH2CH2O) e -(R 62 O) f -R 63 (wherein R 62 represents an alkylene group having 3 or more carbon atoms, R 63 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more.).] Or, the following general formula (5):

Chemical formula

[0049] Examples of compounds represented by the above general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate.

[0050] Examples of oils and fats include vegetable oils and fats, animal oils and fats, vegetable waxes, animal waxes, mineral waxes, and hydrogenated oils.

[0051] In terms of the excellent stability of the dispersion containing organo-modified silicone (α), a combination of a linear or branched alcohol or alkenol having 8 to 24 carbon atoms and a sorbitan ester is more preferred, and a combination of a polyoxyethylene alkyl ether and a sorbitan fatty acid ester is particularly preferred.

[0052] Examples of alkylene oxides include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, and epichlorohydrin. From the viewpoint of minimizing the impact on water repellency and improving the dispersibility (emulsification in one aspect) of the organo-modified silicone (α) or hydrophobic polymer (β), ethylene oxide and 1,2-propylene oxide are preferred as alkylene oxides, with ethylene oxide being more preferred.

[0053] The number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. When the number of moles of alkylene oxide added is within the above range, it is easier to obtain high levels of water repellency and product stability.

[0054] The HLB of the nonionic surfactant is preferably 2 to 18, more preferably 2 to 16. In terms of storage stability of the dispersion, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range. When a nonionic surfactant is used for the dispersion (emulsification in one embodiment) of organo-modified silicone (α), an HLB within the above range is preferable from the viewpoint of obtaining good dispersibility. On the other hand, when a nonionic surfactant is used for the polymerization or dispersion of hydrophobic polymer (β), an HLB of 7 to 18 is preferable from the viewpoint of forming a good aqueous dispersion, and an HLB of 9 to 15 is more preferable when considering the dispersion stability of the liquid polymer (during emulsion polymerization) or solid polymer (during dispersion polymerization) in the composition during emulsion polymerization or dispersion polymerization and after polymerization.

[0055] From the viewpoint of obtaining good dispersion stability (emulsification stability in one embodiment) and water repellency of the dispersion, it is more preferable to use a cationic surfactant and a nonionic surfactant in combination.

[0056] <Hydrophobic polymer (β)> The dispersion preferably further contains a hydrophobic polymer from the viewpoint of initial water repellency and durable water repellency. The hydrophobic polymer may be one or more selected from the group consisting of acrylic polymers and urethane polymers. The dispersion preferably has a pH of 7 or less, more preferably 6 or less, and even more preferably 5 or less.

[0057] [Acrylic polymer] Acrylic polymers are classified by the following general formula (A-1): [ka] [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and, R 2 This represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have substituents. It has constituent units derived from monomer (A-1) (hereinafter also referred to as component (A1)) represented by .

[0058] The hydrophobic polymer (β) may consist only of structural units derived from component (A1) above, or it may further have one or more other structural units. At least one structural unit of the hydrophobic polymer (β) or the monomer corresponding to said structural unit (i.e., forming said structural unit) may have a functional group that can react with a crosslinking agent, for example, at least one functional group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups. In this case, the durable water repellency of the resulting textile product can be further improved. The isocyanate group may form a blocked isocyanate group protected with a blocking agent. If the functional group is an amino group, the texture of the resulting textile product can be further improved.

[0059] (Monomer (A-1)) The above component (A1) has a monovalent hydrocarbon group having 12 or more carbon atoms, which may have substituents. This hydrocarbon group may be linear or branched, saturated or unsaturated, and may also have an alicyclic or aromatic ring. Among these, a linear form is preferred from the viewpoint of water repellency and texture, and a linear alkyl group is more preferred. In this case, water repellency is superior. When the monovalent hydrocarbon group having 12 or more carbon atoms has substituents, examples of substituents include one or more from hydroxyl groups, amino groups, carboxyl groups, epoxy groups, isocyanate groups, blocked isocyanate groups, and (meth)acryloyloxy groups. In this embodiment, in the above general formula (A-1), R 2 It is preferable that the group is an unsubstituted hydrocarbon group.

[0060] From the viewpoint of water repellency, the number of carbon atoms in the hydrocarbon group is preferably 12 to 40, more preferably 12 to 30, and even more preferably 12 to 24. The number of carbon atoms in the hydrocarbon group is particularly preferably 12 to 22. When the number of carbon atoms is within this range, water repellency and texture become particularly excellent. Particularly preferred as the hydrocarbon group is a linear alkyl group with 18 to 22 carbon atoms.

[0061] Examples of the above (A1) component include stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.

[0062] In this disclosure, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester," and the same applies to "(meth)acrylic acid," "(meth)acrylamide," etc.

[0063] The above component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0064] The above component (A1) may be used individually or in combination of two or more types.

[0065] The mass ratio of component (A1) to the total amount of monomer components that are raw materials for the hydrophobic polymer (β) is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, and even more preferably 75 to 98% by mass.

[0066] (Monomer (A-2)) In one embodiment, the acrylic polymer is given by the following general formula (A-2): [ka] [In formula (A-2), R 11 represents a hydrogen atom or a methyl group, R 12 This represents a divalent hydrocarbon group with 1 to 6 carbon atoms. Z represents an ester group or an amide group, and, W is -CO-R 13 (In the formula, R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. ) A group represented by -NH-CO-NH2 group, or the following formula (A-3): [ka] [This represents the base represented by ] The material may further contain constituent units derived from the monomer (A-2) represented by (A1) (hereinafter also referred to as component (A2)). In a preferred embodiment, the material contains component (A2) together with component (A1).

[0067] In general formula (A-2), R 12 These may be linear or branched, saturated or unsaturated hydrocarbon groups, and may even have an alicyclic ring.

[0068] In the above formula (A-2), if Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by -NH-CO-NH2 or the group represented by the above formula (A-3). When Z is an amide group, R 12 is a hydrocarbon group having 2 to 4 carbon atoms, and W is -CO-R 13 It is a group represented by R 13 It is preferable that the carbon number is 1 to 2.

[0069] The above (A2) component is not particularly limited, but examples include diacetone acrylamide, 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl], and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency of textile products, diacetone acrylamide and 2-methylpropenoic acid [2-(2-oxo-2-imidazolidinyl)ethyl] are preferred as the above (A2) component.

[0070] The above component (A2) may be used individually or in combination of two or more types.

[0071] In acrylic polymers, the ratio of constituent units derived from component (A1) to constituent units derived from component (A2) is preferably such that the ratio (A1) / (A2) of the mass of component (A1) to the mass of component (A2) is 99.9 / 0.1 to 70 / 30, more preferably 99.8 / 0.2 to 80 / 20, and even more preferably 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, the durable water repellency and water-repellent properties of the resulting textile product are better.

[0072] The total mass ratio of component (A1) and component (A2) to the total amount of monomer components that are raw materials for the acrylic polymer is preferably 10 to 100% by mass, more preferably 20 to 95% by mass, and even more preferably 30 to 90% by mass.

[0073] (Reactive activator (B)) Acrylic polymers can be obtained in one embodiment by emulsion polymerization or dispersion polymerization. It is preferable that the monomer components that are the raw materials for the acrylic polymer further contain a reactive surfactant (B) (hereinafter also referred to as "component (B)"), in that it can improve the emulsion stability of the polymerized acrylic polymer in the dispersion. That is, it is preferable that the acrylic polymer further has constituent units derived from the reactive surfactant (B). The reactive surfactant (B) is, (B1) When HLB is between 7 and 18, the following general formula (I-1): [ka] [In formula (I-1), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group with 1 to 6 carbon atoms, and Y 1 This represents a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. Compounds represented by, (B2) When HLB is between 7 and 18, the following general formula (II-1): [ka] [In formula (II-1), R 4 Y represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. 2 This represents a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. Compounds represented by, and (B3) Compounds obtained by adding a C2-C4 alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, with an HLB of 7-18. It is at least one species selected from the group consisting of the following:

[0074] In this disclosure, "reactive surfactant" means a surfactant having radical reactivity, more specifically a surfactant having one or more polymerizable unsaturated groups in its molecule, which can be copolymerized with monomers such as (meth)acrylic acid esters.

[0075] Furthermore, through this disclosure, "HLB" is understood to be equivalent to Griffin's HLB, with Griffin's formula modified to the following formula. Here, the hydrophilic group refers to the ethylene oxide group. HLB=(hydrophilic group×20) / molecular weight

[0076] The HLB of the compounds (B1) to (B3) described above is 7 to 18, and 9 to 15 is preferred in terms of emulsion stability (hereinafter simply referred to as emulsion stability) during emulsion polymerization or dispersion polymerization of the acrylic polymer in this embodiment, and in the dispersion after polymerization. Furthermore, in terms of storage stability of the dispersion, it is even more preferable to use two or more reactive activators (B) having different HLBs within the above range in combination.

[0077] In the reactive activator (B1) represented by the above general formula (I-1), R 3 This is a hydrogen atom or a methyl group, and a methyl group is more preferable in terms of copolymerizability with component (A1).

[0078] In general formula (I-1), X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferred in terms of the dispersion (emulsification in one embodiment) stability of the acrylic polymer of this embodiment.

[0079] In general formula (I-1), Y 1 Y is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. 1 The type, combination, and number of alkylene oxy groups in the compound can be appropriately selected within the above HLB range. Furthermore, if there are two or more alkylene oxy groups, they may have a block addition structure or a random addition structure.

[0080] The compound represented by the above general formula (I-1) is the following general formula (I-2): [ka] [In formula (I-2), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group with 1 to 6 carbon atoms. A 1 O represents an alkylene oxy group with 2 to 4 carbon atoms. m is appropriately selected so as to be within the range of the above HLB, and in one embodiment it is an integer from 1 to 80, and when m is 2 or greater there are m A 1 O may be the same or different. Compounds represented by are preferred.

[0081] In general formula (I-2), R 3 This is a hydrogen atom or a methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A1).

[0082] In general formula (I-2), X is a linear or branched alkylene group having 1 to 6 carbon atoms, and a linear alkylene group having 2 to 3 carbon atoms is more preferable in terms of the dispersion (emulsification in one embodiment) stability of the acrylic polymer of this embodiment.

[0083] In general formula (I-2), A 1 O is an alkylene oxy group with 2 to 4 carbon atoms. 1 The type and combination of O, and the number of m, can be appropriately selected so as to be within the above HLB range. In terms of dispersion (emulsification in one embodiment) stability of the acrylic polymer in this embodiment, m is preferably an integer from 1 to 80, and more preferably an integer from 1 to 60. When m is 2 or more, m A 1 O may be the same or different. Also, A 1 If there are two or more types of oxygen, they can have a block-type or random-type structure.

[0084] The component (B1) represented by the above general formula (I-2) can be obtained by conventionally known methods and is not particularly limited. It can also be more readily obtained than commercially available products, for example, "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0085] In the (B2) component represented by the above general formula (II-1) used in this embodiment, R 4This is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, such as tridecenyl group, tridecadienyl group, tetradecenyl group, tetradecenyl group, pentadecenyl group, pentadecadienyl group, pentadecatrienyl group, heptadedecenyl group, heptadecadienyl group, heptadecatrienyl group, etc. In terms of the dispersion (emulsification in one embodiment) stability of the acrylic polymer of this embodiment, R 4 A monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms is more preferable.

[0086] Y 2 Y is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. 2 The type, combination, and number of alkylene oxy groups in the compound can be appropriately selected so as to be within the above HLB range. Furthermore, if there are two or more alkylene oxy groups, they can have a block addition structure or a random addition structure. In terms of dispersion (emulsification in one embodiment) stability of the acrylic polymer in this embodiment, ethylene oxy groups are more preferred.

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

[0088] [ka] [In formula (II-2), R 4 This represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. A 2 O represents an alkylene oxy group with 2 to 4 carbon atoms. n can be appropriately selected so as to be within the range of the above HLB, and specifically, an integer from 1 to 50 is preferred, and when n is 2 or more, n A 2 O may be the same or different. Compounds represented by are preferred.

[0089] In the compound represented by the above general formula (II-2), R 4This is R in the general formula (II-1) described above. 4 Similar examples include the above.

[0090] A 2 O is an alkylene oxy group having 2 to 4 carbon atoms. In terms of the dispersion (emulsification in one embodiment) stability of the acrylic polymer of this embodiment, A 2 The type and combination of O, and the number of n can be appropriately selected so as to be within the range of HLB described above. In terms of the dispersion (emulsification in one embodiment) stability of the acrylic polymer in this embodiment, A 2 O is more preferably an ethylene oxy group, n is preferably an integer from 1 to 50, more preferably an integer from 5 to 20, and even more preferably an integer from 8 to 14. When n is 2 or more, there are n A 2 O may be the same or different. Also, A 2 If there are two or more types of oxygen, they can have a block-type or random-type structure.

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

[0092] The phenols having the corresponding unsaturated hydrocarbon groups mentioned above include not only industrially produced pure products or mixtures, but also those that exist 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, and 3-[11(Z)-pentadecenyl]phenol, which are extracted from cashew nut shells, etc., and collectively known as cardanol.

[0093] The (B3) component used in this embodiment is a compound obtained 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. Examples of the oil or fat having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids which may contain hydroxy unsaturated fatty acids (such as 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 hydroxy unsaturated fatty acid (such as ricinoleic acid, ricinelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of the dispersion (in one aspect, emulsification) stability of the acrylic polymer of this embodiment, an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferable, an alkylene oxide adduct having 2 to 4 carbon atoms of castor oil (a triglyceride of a fatty acid containing ricinoleic acid) is more preferable, and an ethylene oxide adduct of castor oil is even more preferable. Further, the number of moles of the added alkylene oxide can be appropriately selected so as to be within the above HLB range. From the viewpoint of the dispersion (in one aspect, emulsification) stability of the acrylic polymer of this embodiment, 20 to 50 moles is more preferable, and 25 to 45 moles is even more preferable. When two or more kinds of alkylene oxides are used, they can have a block addition structure or a random addition structure.

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

[0095] In the acrylic polymer of the present embodiment, the compositional ratio of the monomer of the component (B) is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass with respect to the total amount of the monomer components constituting the acrylic polymer, from the viewpoint of improving the water repellency of the obtained fiber product and the emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic polymer of the present embodiment.

[0096] (Monomer (C)) The acrylic polymer preferably further contains a structural unit derived from at least one monomer (C) (hereinafter also referred to as component (C)) selected from the group consisting of the following (C1), (C2), (C3) and (C4) in terms of improving the durable water repellency of the obtained fiber product.

[0097] (C1) The following general formula (C-1): [Chemical formula] [In formula (C-1), R 5 represents a hydrogen or methyl group, and R 6 represents a monovalent chain hydrocarbon group having 1 to 11 carbon atoms 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.] The (meth)acrylic acid ester monomer represented by (hereinafter also referred to as component (C1)).

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

[0099] (C3) The following general formula (C-3): [ka] [In formula (C-3), R 9 This represents an unsubstituted, monovalent, chain-like hydrocarbon group with 1 to 4 carbon atoms. A methacrylate monomer represented by (hereinafter also referred to as the (C3) component)

[0100] (C4) The following general formula (C-4): [ka] [In formula (C-4), R 10 [where 'p' represents a hydrogen or methyl group, 'p' represents an integer greater than or equal to 2, 'S' represents a (p+1) valent organic group, and 'T' represents a monovalent organic group having a polymerizable unsaturated group.] (Meth)acrylic acid ester monomers represented by (hereinafter also referred to as (C4) component)

[0101] The above (C1) component is a (meth)acrylic acid ester monomer having a monovalent linear hydrocarbon group having 1 to 11 carbon atoms, with the ester portion 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. From the viewpoint of being receptive to crosslinking agents, it is preferable that the above monovalent linear hydrocarbon group having 1 to 11 carbon atoms 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 an acrylic polymer having structural units derived from these crosslinking agent-receptive (C1) components is treated with a crosslinking agent to a textile product, 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.

[0102] The above-mentioned linear hydrocarbon group may be linear or branched, and may be saturated or unsaturated hydrocarbon group. Furthermore, the linear hydrocarbon group may have substituents in addition to the above-mentioned functional group. Among these, being linear and / or saturated hydrocarbon groups is preferable in that it can improve the durable water repellency of the resulting textile product.

[0103] Specific examples of the (C1) component include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used individually or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred for their ability to improve the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred for its ability to improve the texture of the resulting textile product.

[0104] The mass of component (C1) to be added is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency. The mass of component (C1) to be added is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency.

[0105] The above (C2) component is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester portion. Examples of cyclic hydrocarbon groups include isobornyl, cyclohexyl, and dicyclopentanyl groups. These cyclic hydrocarbon groups may have substituents such as alkyl groups. However, if the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the sum of the number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. Furthermore, it is preferable from the viewpoint of improving durable water repellency that these cyclic hydrocarbon groups are directly bonded to the ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used individually or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred, as they can improve the durable water repellency of the resulting textile products.

[0106] The mass of component (C2) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency. The mass of component (C2) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency.

[0107] The above (C3) component is a methacrylic acid ester monomer in which a monovalent linear hydrocarbon group having 1 to 4 carbon atoms without substitution is directly bonded to an ester bond in the ester moiety. As the linear hydrocarbon group having 1 to 4 carbon atoms, a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable. Examples of the linear 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, a t-butyl group, and the like. Specific compounds 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 them, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferable, and methyl methacrylate is more preferable in terms of improving the durable water repellency of the resulting fiber product.

[0108] From the viewpoint of water repellency, the mass of the (C3) component to be blended is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the (A1) component to be blended. From the viewpoint of water repellency, the mass of the (C3) component to be blended is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, based on 100 parts by mass of the (A1) component to be blended.

[0109] The above (C4) component is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In this embodiment, a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, where T in the above general formula (C-4) is a (meth)acryloyloxy group, is preferred. In general formula (C-4), the p Ts may be the same or different. Specific compounds include, for example, 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 individually or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred because they can improve the durable water repellency of the resulting textile products.

[0110] The mass of component (C4) to be added is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency. The mass of component (C4) to be added is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency.

[0111] The mass of component (C) to be added is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency. The mass of component (C) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of component (A1) to be added, from the viewpoint of water repellency.

[0112] (Monomer (VC)) From the viewpoint of peel strength, the acrylic polymer preferably further contains constituent units derived from monomers (VC) (hereinafter also referred to as "(VC) component") selected from the group consisting of vinyl chloride and vinylidene chloride.

[0113] (VC) From the viewpoint of maintaining the texture of textile products, vinyl chloride is preferred as the (VC) component.

[0114] The amount of (VC) component to be added is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of (A1) component to be added, from the viewpoint of water repellency, durable water repellency, and peel strength. The mass of the (VC) component to be added is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, per 100 parts by mass of (A1) component to be added, from the viewpoint of water repellency, durable water repellency, and texture.

[0115] (Monomer (D)) The acrylic polymer may further contain constituent units derived from a monofunctional monomer (D) (hereinafter also referred to as component (D)) copolymerizable with component (A1), to the extent that it does not impair the effects of the present invention.

[0116] Examples of component (D) include vinyl monomers other than component (VC) that do not contain fluorine, such as (meth)acryloylmorpholine, (meth)acrylic acid esters having hydrocarbon groups, (meth)acrylic acid, fumarate esters, maleate esters, fumarate, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, and styrene. Note that (meth)acrylic acid esters having hydrocarbon groups may have substituents on the hydrocarbon group such as vinyl groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and blocked isocyanate groups, or substituents other than groups that can react with crosslinking agents, such as quaternary ammonium groups, and may have ether bonds, ester bonds, amide bonds, or urethane bonds. Examples of (meth)acrylic acid esters include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Among these, (meth)acryloylmorpholine is more preferred because it can improve the peel strength of the coating on the resulting textile product.

[0117] In this embodiment, the weight-average molecular weight of the acrylic polymer is preferably 30,000 or more. When the weight-average molecular weight is 30,000 or more, the water repellency of the resulting textile product tends to improve further. Furthermore, the weight-average molecular weight of the acrylic polymer is more preferably 100,000 or more. In this case, the resulting textile product can exhibit even greater water repellency. The upper limit of the weight-average molecular weight of the acrylic polymer is preferably around 5 million.

[0118] In this disclosure, the weight-average molecular weight of an acrylic polymer is measured using a GPC (gel permeation chromatography) apparatus (for example, the 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 the eluent, and the value is expressed in terms of standard polystyrene. The column used is a combination of three columns manufactured by Tosoh Corporation, product names TSK-GEL G5000HHR, G4000HHR, and G3000HHR.

[0119] The melt viscosity of the acrylic polymer at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, it tends to be easier to maintain a good texture in the resulting textile product. Furthermore, when the melt viscosity of the acrylic polymer is 1000 Pa·s or less, it is possible to suppress the precipitation or sedimentation of the acrylic polymer when it is dispersed (emulsified in one embodiment) to form a dispersion, thus tending to maintain a good storage stability in the dispersion. More preferably, the melt viscosity at 105°C is 500 Pa·s or less. In this case, the resulting textile product will exhibit sufficient water repellency while also having a superior texture. From the viewpoint of water repellency, the melt viscosity of the acrylic polymer at 105°C may be, for example, 10 Pa·s or more, 50 Pa·s or more, or 100 Pa·s or more.

[0120] "Melting viscosity at 105°C" is determined by using an elevated flow tester (e.g., Shimadzu CFT-500), placing 1 g of acrylic polymer into a cylinder fitted with a die (10 mm long, 1 mm in diameter), holding it at 105°C for 6 minutes, and measuring the viscosity using a plunger at 100 kg·f / cm². 2 This refers to the viscosity measured when a load is applied.

[0121] [Urethane polymer] Examples of urethane polymers include hydrophobic compounds having structural units derived from a polyfunctional compound represented by the following general formula (UI-1) and structural units derived from an isocyanate compound represented by the following general formula (UII).

[0122] R U31 [-W 1 -R U32 ] d [-V 1 ] e (UI-1) [In equation (UI-1), d represents an integer greater than or equal to 1, e represents an integer greater than or equal to 2, and (d+e) is between 3 and 6, R U31 represents an organic group with (d+e) valency, W 1R represents a divalent group which is an ester group, amide group, urethane group, or urea group. U32 represents a monovalent hydrocarbon group with 8 to 24 carbon atoms in a straight or branched chain, V 1 V represents a hydroxyl group, amino group, or carboxyl group. However, e V 1 Two or more of these are hydroxyl groups and / or amino groups.

[0123] R U33 [-NCO] f (UII) [In formula (UII), R U33 [where f represents an f-valent organic group, and f represents an integer from 2 to 7.]

[0124] Such hydrophobic compounds can be obtained by reacting at least a polyfunctional compound represented by the above general formula (UI-1) with an isocyanate compound represented by the above general formula (UII).

[0125] In this disclosure, an ester group means a group represented by -O-CO-. An amide group means a group represented by -NH-CO-. A urethane group means a group represented by -O-CO-NH-. A urea group means a group represented by -NH-CO-NH-. An isocyanate group means a group represented by -N=C=O. A carbonyl group means a group represented by -CO-.

[0126] First, we will explain the polyfunctional compound represented by the general formula (UI-1) above.

[0127] In the above general formula (UI-1), if d is 2 or greater, there are multiple W 1 They may be the same or different, and there may be multiple R U32 V may be the same or different, and there may be multiple V 1 They may be the same or different.

[0128] R U31 represents an organic group with a (d+e) valency. From the viewpoint of water repellency, durable water repellency (especially washability) and water penetration prevention, R U31The number of carbon atoms is preferably 2 to 40, and more preferably 4 to 12. U31 For example, see the following chemical formula (7): [ka] The group represented by the following chemical formula (8): [ka] The group represented by the following chemical formula (9): [ka] [In equation (9), m1 represents an integer greater than or equal to 1.] A base represented by is preferred.

[0129] (d+e) is preferably 3 to 4 from the viewpoint of ease of handling the polymer. m1 represents an integer greater than or equal to 1, preferably between 1 and 3.

[0130] R U31 This may be a residue obtained by removing (d+e) functional groups from a polyfunctional organic compound (hereinafter referred to as "polyfunctional compound A") having (d+e) at least one functional group selected from the group consisting of hydroxyl groups, amino groups, and carboxyl groups, provided that two or more of the (d+e) functional groups are hydroxyl groups and / or amino groups.

[0131] Examples of polyfunctional compound A include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, aminoethylethanolamine, diethanolamine, and triethanolamine. Among these, trimethylolpropane, ditrimethylolpropane, diethanolamine, and diethylenetriamine are preferred from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, and dispersion stability of hydrophobic compounds.

[0132] W 1 W represents a divalent group that is an ester group, amide group, urethane group, or urea group. 1 From the viewpoint of water repellency, durable water repellency (especially washability), and water penetration prevention, it is preferable that the material be an ester group or a urethane group.

[0133] R U32 This represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may also have an alicyclic or aromatic ring. As for the hydrocarbon group, a linear form is preferred, and a linear alkyl group is more preferred, as it provides superior water repellency. The number of carbon atoms in the hydrocarbon group is preferably 10 to 24, more preferably 12 to 22, and particularly preferably 12 to 18. When the number of carbon atoms is within this range, water repellency and texture are particularly excellent. As for the hydrocarbon group, a linear alkyl group having 12 to 18 carbon atoms is particularly preferred.

[0134] R U32 Examples of such groups include nonyl, decyl, undecyl, dodecyl (lauryl), myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, heneicosyl, and behenyl groups.

[0135] R U32 This may be a residue obtained by removing the reactive group from a reactive hydrocarbon compound that has a reactive group capable of reacting with the functional group of the polyfunctional compound A described above. Examples of reactive hydrocarbon compounds include higher fatty acids (including the carbonyl group) having 8 to 24 carbon atoms, higher aliphatic alcohols, higher aliphatic monoisocyanates, and higher aliphatic amines.

[0136] Examples of high-grade fatty acids include lauric acid, myristic acid, pentadecyl acid, palmitic acid, heptadecanoic acid, stearic acid, oleic acid, eicosanoic acid, and docosanoic acid.

[0137] Examples of higher aliphatic alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, eicosanol, heneicosanol, and behenyl alcohol.

[0138] Examples of higher aliphatic monoisocyanates include decyl isocyanates, undecyl isocyanates, dodecyl isocyanates, myristyl isocyanates, pentadecyl isocyanates, cetyl isocyanates, stearyl isocyanates, eicosyl isocyanates, and behenyl isocyanates.

[0139] Examples of higher aliphatic amines include decylamine, laurylamine, myristylamine, stearylamine, and behenylamine.

[0140] V 1 V represents a hydroxyl group, an amino group, or a carboxyl group. 1 From the viewpoint of durable water repellency, it is preferable that the group be a hydroxyl group or an amino group.

[0141] The polyfunctional compound represented by the above general formula (UI-1) is, for example, a polyfunctional organic compound (polyfunctional compound A) having (d+e) at least one functional group selected from the group consisting of hydroxyl groups, amino groups, and carboxyl groups, and [-W 1 -R U32 It can be produced by introducing d hydrophobic groups represented by ].

[0142] [-W 1 -R U32 The hydrophobic group represented by ] can be introduced, for example, by reacting 1 mole or more of the reactive hydrocarbon compound with 1 mole of the polyfunctional compound A, using conventionally known synthesis methods, i.e., esterification, amidation, or urethane reaction, such that the number of unreacted functional groups e of the polyfunctional compound A is 2 or more.

[0143] The polyfunctional compound represented by the above general formula (UI-1) is not particularly limited, but it is preferably at least one selected from the group consisting of the polyfunctional compound represented by the following general formula (UI-2), the polyfunctional compound represented by the following general formula (UI-3), and the polyfunctional compound represented by the following general formula (UI-4).

[0144] C[-R 41 ] g [-R 42 -V 2 ] h [-R 43 -W 2 -R 44 ] i (UI-2) [In equation (UI-2), g is an integer of 0 or 1, h is an integer of 2 or 3, i is an integer of 1 or 2, (g+h+i) is 4, R 41 R represents a straight-chain or branched hydrocarbon group having 1 to 4 carbon atoms. 42 R represents a divalent alkylene group with 1 to 2 carbon atoms. 43 R represents a divalent alkylene group with 1 to 4 carbon atoms. 44 represents a monovalent hydrocarbon group with 8 to 24 carbon atoms in a straight or branched chain, W 2 V represents a divalent group which is an ester group, amide group, urethane group, or urea group. 2 V represents a hydroxyl group, an amino group, or a carboxyl group. However, two or more V 2 [These are hydroxyl groups and / or amino groups.]

[0145] [ka] [In formula (UI-3), R 51 and R 52 Each of these independently represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 54 and R 55 Each of these independently represents a divalent alkylene group with 1 to 4 carbon atoms, and R 53 , R 56 , R 57 and R 58Each of these independently represents a monovalent group represented by the following general formula (I-3a) or the following general formula (I-3b). -R 59 -V 3 (I-3a) {R 59 represents a divalent alkylene group with 1 to 4 carbon atoms, V 3 This represents a hydroxyl group, an amino group, or a carboxyl group. -R 60 -W 3 -R 61 (I-3b) {R 60 R represents a divalent alkylene group with 1 to 4 carbon atoms. 61 represents a monovalent hydrocarbon group with 8 to 24 carbon atoms in a straight or branched chain, W 3 This represents a divalent group, such as an ester group, amide group, urethane group, or urea group. However, R 53 , R 56 , R 57 and R 58 At least two of them are V 3 This is a group represented by the general formula (I-3a) above, where is a hydroxyl group or an amino group.

[0146] [ka] [In equation (UI-4), j represents an integer from 1 to 4, R 71 and R 73 Each of these independently represents a divalent alkylene group with 1 to 4 carbon atoms, and R 72 and R 74 Each of these independently represents a hydroxyl group, an amino group, or a monovalent group represented by the following general formula (I-4a), R 75 represents hydrogen, a monovalent group represented by the following general formula (I-4b), general formula (I-4c), or general formula (I-4d). -W 4 -R 76 (I-4a) {In formula (I-4a), W 4 R represents a divalent group which is an ester group, amide group, urethane group, or urea group. 76This represents a monovalent hydrocarbon group with 8 to 24 carbon atoms, either linear or branched. -R 77 -OH (I-4b) {In formula (I-4b), R 77 This represents an alkylene group with 2 to 3 carbon atoms. -R 78 -W 5 -R 79 (I-4c) {In formula (I-4c), R 78 R represents an alkylene group with 2 to 3 carbon atoms. 79 represents a monovalent hydrocarbon group with 8 to 24 carbon atoms in a straight or branched chain, W 5 This indicates a divalent group, which is an ester group, amide group, urethane group, or urea group. -W 6 -R 80 (I-4d) {In formula (I-4d), W 6 R represents a carbonyl group or an amide group. 80 This represents a monovalent hydrocarbon group with 8 to 24 carbon atoms, either linear or branched. However, R 72 , R 74 and j R 75 At least two of these are a hydroxyl group, an amino group, hydrogen, and a monovalent group represented by the general formula (I-4b) above, R 72 and R 74 is a hydroxyl group or an amino group, R 75 [This is hydrogen or a monovalent group represented by the general formula (I-4b) above.]

[0147] In the polyfunctional compound represented by the above general formula (UI-2), if i is 2, there are multiple W 2 They may be the same or different. If i is 2, there may be multiple R 43 They may be the same or different. If i is 2, there may be multiple R 44 They may be the same or different. 44 This is R in the above general formula (UI-1). U32 This corresponds to multiple R versions. 42 They may be the same or different. There may be multiple V 2They may be the same or different.

[0148] In the polyfunctional compound represented by the above general formula (UI-2), W 2 W is a divalent group that is an ester group, amide group, urethane group, or urea group. 2 From the viewpoint of water repellency, durable water repellency (especially washability), and water penetration prevention, it is preferable that the material be an ester group or a urethane group.

[0149] In the polyfunctional compound represented by the above general formula (UI-2), V 2 This is a hydroxyl group, an amino group, or a carboxyl group. 2 From the viewpoint of durable water repellency, it is preferable that the group be a hydroxyl group or an amino group.

[0150] In the group represented by the above general formula (I-3a), V 3 This is a hydroxyl group, an amino group, or a carboxyl group. 3 From the viewpoint of durable water repellency, it is preferable that the group be a hydroxyl group or an amino group.

[0151] In the group represented by the above general formula (I-3b), R 61 R is a monovalent hydrocarbon group having 8 to 24 carbon atoms, either linear or branched. 61 This is R in the above general formula (UI-1). U32 It corresponds to.

[0152] In the group represented by the above general formula (I-3b), W 3 W is a divalent group that is an ester group, amide group, urethane group, or urea group. 3 From the viewpoint of water repellency, durable water repellency (especially washability), and water penetration prevention, it is preferable that the material be an ester group or a urethane group.

[0153] In the group represented by the above general formula (I-4a), R 76 R is a monovalent hydrocarbon group having 8 to 24 carbon atoms, either linear or branched. 76 This is R in the above general formula (UI-1). U32 It corresponds to.

[0154] In the group represented by the above general formula (I-4a), W 4 W is a divalent group that is an ester group, amide group, urethane group, or urea group. 4 From the viewpoint of water repellency, durable water repellency (especially washability), and water penetration prevention, it is preferable that the group be an ester group, an amide group, or a urethane group.

[0155] In the group represented by the above general formula (I-4b), R 79 R is a monovalent hydrocarbon group having 8 to 24 carbon atoms, either linear or branched. 79 This is R in the above general formula (UI-1). U32 It corresponds to.

[0156] In the group represented by the above general formula (I-4c), W 5 W is a divalent group that is an ester group, amide group, urethane group, or urea group. 5 From the viewpoint of water repellency, durable water repellency (especially washability), and water penetration prevention, it is preferable that the group be an ester group, an amide group, or a urethane group.

[0157] In the group represented by the above general formula (I-4d), R 80 R is a monovalent hydrocarbon group having 8 to 24 carbon atoms, either linear or branched. 80 This is R in the above general formula (UI-1). U32 It corresponds to.

[0158] Next, we will explain isocyanate compounds represented by the above general formula (UII).

[0159] R U33 R represents an f-valent organic group. U33 The number of carbon atoms is preferably 4 to 40, and more preferably 6 to 18, from the viewpoint of water repellency, durable water repellency (especially washability) and water penetration prevention. U33 A hexylene group is preferred. f may be an integer from 2 to 7, and is preferably 2 to 3 from the viewpoint of water repellency, durable water repellency (especially washability) and water penetration prevention.

[0160] The isocyanate compound represented by the above general formula (UII) may be a polyisocyanate compound. Examples of polyisocyanate compounds include liquid MDI represented by tolylene diisocyanate, diphenylmethane diisocyanate (MDI), polyphenylpolymethyl polyisocyanate, crude MDI, diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate, as well as trimers of these which are isocyanurate rings. Among these, hexamethylene diisocyanate is preferred from the viewpoint of water repellency, durable water repellency (especially washability) and water penetration prevention.

[0161] Examples of hydrophobic compounds obtained by reacting a polyfunctional compound represented by the above general formula (UI-1) with an isocyanate compound represented by the above general formula (UII) include hydrophobic compounds having substructures represented by the following general formulas (UIII-1), (UIII-2), or (UIII-3).

[0162] [ka] [In equation (UIII-1), n1 represents an integer greater than or equal to 2, R 91 and R 92 Each of these independently represents a monovalent hydrocarbon group having 10 to 24 carbon atoms, either linear or branched.

[0163] n1 represents an integer of 2 or more, and is preferably between 2 and 100, and more preferably between 2 and 50, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0164] [ka] [In equation (UIII-2), n2 represents an integer greater than or equal to 2, n3 represents an integer greater than or equal to 1, R 93 Each of these independently represents a monovalent hydrocarbon group having 10 to 24 carbon atoms, either linear or branched.

[0165] n2 represents an integer of 2 or more, and is preferably between 2 and 200, and more preferably between 2 and 100, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0166] n3 represents an integer greater than or equal to 1, and is preferably between 1 and 3, and more preferably 1, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, and dispersion stability of hydrophobic compounds.

[0167] [ka] [In equation (UIII-3), n4 represents an integer greater than or equal to 2, R 94 Each of these independently represents a monovalent hydrocarbon group having 10 to 24 carbon atoms, either linear or branched.

[0168] n4 represents an integer of 2 or more, and is preferably between 2 and 200, and more preferably between 2 and 100, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0169] Examples of hydrophobic compounds having the substructure represented by the above general formula (UIII-1) include the compound represented by the following formula (UIII-4).

[0170] [ka] [In equation (UIII-4), n5 represents an integer greater than or equal to 2, R X This is expressed by the following formula (R-1):

[0171] [ka] This represents a monovalent organic group.

[0172] n5 represents an integer of 2 or more, and is preferably between 2 and 100, and more preferably between 2 and 50, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0173] Examples of hydrophobic compounds having the substructure represented by the above general formula (UIII-2) include the compound represented by the following formula (UIII-5).

[0174] [ka] [In equation (UIII-5), n6 represents an integer greater than or equal to 2, and n7 represents an integer greater than or equal to 1. R X This represents a monovalent organic group represented by the above formula (R-1).

[0175] n6 represents an integer of 2 or more, and is preferably between 2 and 200, and more preferably between 2 and 100, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0176] n7 represents an integer greater than or equal to 1, and is preferably 1 to 3, and more preferably 1, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, and dispersion stability of hydrophobic compounds.

[0177] Examples of hydrophobic compounds having the substructure represented by the above general formula (UIII-3) include the compound represented by the following formula (UIII-6).

[0178] [ka] [In equation (UIII-6), n8 represents an integer greater than or equal to 2, R XThis represents a monovalent organic group represented by the above formula (R-1).

[0179] n8 represents an integer of 2 or more, and is preferably between 2 and 200, and more preferably between 2 and 100, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, dispersion stability of hydrophobic compounds, and ease of handling of polymers.

[0180] From the viewpoint of chemical resistance, the hydrophobic compound according to this embodiment preferably has blocked isocyanate groups protected with a blocking agent. From the viewpoint of chemical resistance, the ratio of blocked isocyanate groups to the total number of isocyanate groups and blocked isocyanate groups contained in the hydrophobic compound is preferably 80% or more, more preferably 90% or more, and even more preferably 100%.

[0181] Examples of blocked isocyanate groups protected with a blocking agent include the following general formula: (-NH-CO-B) [In the formula, B is a group derived from a blocking agent.] Examples of groups represented by the following are given.

[0182] Examples of blocking agents include pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazoles; alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, and tert-butyl alcohol; and phenols such as phenol, methylphenol, chlorophenol, p-iso-butylphenol, p-tert-butylphenol, p-iso-amylphenol, p-octylphenol, and p-nonylphenol. Examples include active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldehyde, acetaldehyde, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; N-substituted amides such as N-methylacetamide and acetanilide; imide compounds such as succinimide and phthalimide; and imidazole compounds such as imidazole and 2-methylimidazole. The blocking agent may be used alone or in combination of two or more types. Among these, from the viewpoint of versatility, the reactivity of the blocked isocyanate group, and ease of blocking, it is preferable to use at least one compound selected from the group consisting of pyrazoles, oximes, and lactams, and more preferably to use at least one compound selected from the group consisting of dimethylpyrazole, methyl ethyl ketone oxime, and caprolactam.

[0183] The weight-average molecular weight (Mw) of the hydrophobic compound in this embodiment is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000, from the viewpoint of water repellency, durable water repellency (especially washability), water penetration prevention, and dispersion stability of the hydrophobic compound. The weight-average molecular weight of the hydrophobic compound is measured by GPC (gel permeation chromatography) and is the value converted to standard polystyrene.

[0184] When reacting a polyfunctional compound represented by the general formula (UI-1) having e hydroxyl groups and / or amino groups with a compound represented by the general formula (UII), the amount of the compound represented by the general formula (UII) is preferably (0.8 to 1.20) × 2 / e moles, more preferably (0.80 to 0.99) × 2 / e moles, and even more preferably (0.85 to 0.95) × 2 / e moles) per mole of the polyfunctional compound represented by the general formula (UI-1). Alternatively, (1.01 to 1.20) × 2 / e moles is more preferably (1.05 to 1.15) × 2 / e moles.

[0185] In the dispersion, the amount of hydrophobic polymer (β) relative to 100 parts by mass of the total of organo-modified silicone (α) and hydrophobic polymer (β) is preferably 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more, from the viewpoint of initial water repellency and durable water repellency, and preferably 99 parts by mass or less, 95 parts by mass or less, or 90 parts by mass or less.

[0186] <Liquid medium> In a typical embodiment, the dispersion contains a liquid medium. In a typical embodiment, the liquid medium contains water and optionally further contains an organic solvent. In one embodiment, the ratio of water to 100% by mass of the total liquid medium is 50% by mass or more. The amount of liquid medium in the dispersion may be adjusted so that the content of organo-modified silicone (α) and any other components in the dispersion is within a desired range.

[0187] [Poorly water-soluble organic solvents] In one embodiment, the dispersion contains, as a liquid medium, an organic solvent (hereinafter also referred to as a poorly water-soluble organic solvent) in which the amount of water required to dissolve 1 g of the organic solvent at 20°C is more than 10 mL. In one embodiment, the amount of water required to dissolve 1 g of the organic solvent is more than 30 mL, preferably more than 100 mL, and more preferably more than 1000 mL. Such a poorly water-soluble organic solvent contributes to the stable dispersion of organo-modified silicone (α) (for example, the formation of an emulsion in which organo-modified silicone (α) is stably dispersed), and therefore contributes to the formation of a dispersion with excellent storage stability. The amount of water required to dissolve 1 g of the organic solvent is a value measured by the following method in accordance with JIS K8001:2017.

[0188] In accordance with JIS K8001:2017 3.2 "Terminology for Describing the Degree of Solubility," 1 g of organic solvent is placed in a fixed amount of water and shaken vigorously for 30 seconds every 5 minutes at 20°C ± 5°C. The volume of water (mL) required for the solvent to dissolve within 30 minutes is evaluated. In this measurement, 1 mL, 10 mL, 30 mL, 100 mL, or 1000 mL of water is used as the fixed amount of water, and it is investigated whether 1 g of organic solvent dissolves within 30 minutes under the above conditions. The evaluation criteria are as follows. (Evaluation criteria for the amount of water required to dissolve 1g of organic solvent) Less than 1 mL: Dissolved in 1 mL of water within 30 minutes. For concentrations between 1 mL and 10 mL: It did not dissolve in 1 mL of water within 30 minutes, but it dissolved in 10 mL of water within 30 minutes. Over 10 mL and up to 30 mL: It did not dissolve in 10 mL of water within 30 minutes, but it dissolved in 30 mL of water within 30 minutes. For concentrations between 30 mL and 100 mL: It did not dissolve in 30 mL of water within 30 minutes, but it dissolved in 100 mL of water within 30 minutes. For concentrations between 100 mL and 1000 mL: It did not dissolve in 100 mL of water within 30 minutes, but it did dissolve in 1000 mL of water within 30 minutes. Over 1000mL: It did not dissolve in 1000mL of water within 30 minutes.

[0189] The following are examples of the amount of water required to dissolve 1g of an organic solvent. • Isoparaffin (isoparaffin with 10-16 carbon atoms): over 1000 mL • Mineral oil (kinematic viscosity at 30°C: 20 mm²) 2 / s):More than 1000mL • Mineral spirits (boiling point: 180-200°C): over 1000mL • Ester (2,2,4-trimethyl-1,3-pentanediol diisobutyrate): over 1000mL • Tripropylene glycol (TPG): 1 mL or less • Dipropylene glycol (DPG): 1 mL or less • Butyl diglycol: 1 mL or less

[0190] Although not bound by theory, it is presumed that when dispersing organo-modified silicone (α) in a water-containing medium during the production of a dispersion (in one embodiment, when forming an emulsion containing organo-modified silicone (α)), poorly water-soluble organic solvents contribute to improving the dispersion stability (in one embodiment, emulsion stability) of organo-modified silicone (α) in a water-containing medium by promoting the dispersion (in one embodiment, O / W type emulsion).

[0191] In terms of its effect on improving the dispersion stability of organo-modified silicone (α), it is preferable that poorly water-soluble organic solvents have a structure composed of carbon and hydrogen (i.e., a hydrocarbon structure) within the molecule. From this viewpoint, preferred poorly water-soluble organic solvents include, for example, esters (specific examples: 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl acetate, butyl acetate, butyl glycol acetate, etc.), ketones (specific examples: methyl isobutyl ketone, etc.), and ethers (specific examples: dibutyl diglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethyl glycol monohexyl ether, etc.). These may be ethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, etc., alcohols (specific examples include 1-butanol, 1-pentanol, isooctanool, etc.), aromatic solvents (specific examples include toluene, o-xylene, m-xylene, p-xylene, mesitylene, etc.), petroleum solvents (specifically, isoparaffin, mineral oil, mineral spirits, synthetic oils such as poly-αolefins, etc.), and these organic solvents can be used individually or in combination of two or more.

[0192] The isoparaffin has preferably 4 or more carbon atoms, and more preferably 9 to 20 carbon atoms. Examples of such isoparaffins include IP Solvent IP-2028 (an isoparaffin with 10 to 16 carbon atoms, manufactured by Idemitsu Kosan Co., Ltd.).

[0193] As a mineral oil, its kinematic viscosity at 30°C is 50 mmHg. 2Examples of mineral oils with a kinematic viscosity of 1 / s or less include n-undecane, n-dodecane, n-tridecane, n-tetradecane, paraffin, etc. The above kinematic viscosity is measured according to the method conforming to JIS K 2283:2000. The number of carbon atoms in paraffin may be, for example, 10 to 16. Mineral oils may be used alone or in combination of two or more types. In the case of a combination of two or more types, it is preferable that they are mutually compatible. Mineral oils may be commercially available products, for example, Cactus Normal Paraffin N-12D, Cactus Normal Paraffin YHNP, Cactus Normal Paraffin N-14 (all available from ENEOS Corporation), etc.

[0194] For mineral spirits, those with a boiling point of 130-230°C are particularly preferred.

[0195] The amount of poorly water-soluble organic solvent in the dispersion is preferably 0.5 to 500 parts by mass, more preferably 1 to 400 parts by mass, even more preferably 1 to 300 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of organo-modified silicone (α), from the viewpoint of dispersion stability of the organo-modified silicone (α). The amount of poorly water-soluble organic solvent is preferably within the above range in terms of good storage stability and good water repellency of the dispersion.

[0196] <Water-soluble organic solvents> The dispersion of this embodiment may further contain a water-soluble organic solvent in addition to the poorly water-soluble organic solvent as a liquid medium. In this disclosure, a water-soluble organic solvent means an organic solvent that, as evaluated by the method described above in accordance with JIS K8001:2017, requires 10 mL or less of water to dissolve 1 g of the organic solvent at 20°C. Examples of water-soluble organic solvents include dipropylene glycol, tripylene glycol, butyl diglycol, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran, with dipropylene glycol, tripylene glycol, and butyl diglycol being particularly preferred.

[0197] <Additional ingredients> The dispersion of this embodiment may contain additional components. Examples of additional components include additional water-repellent and / or oil-repellent components, initiators, chain transfer agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insecticides, defoamers, etc. Examples of additional water-repellent and / or oil-repellent components include waxes (e.g., paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, etc.), animal and plant waxes, and mineral waxes.

[0198] The total concentration of organo-modified silicone (α) and hydrophobic polymer (β) in the dispersion (or the concentration of organo-modified silicone (α) alone if hydrophobic polymer (β) is not used) may be appropriately changed depending on the application, but may be, for example, 0.01 to 70% by mass, or 0.05 to 50% by mass. The concentration of the above-mentioned <additional components> in the dispersion may be appropriately changed depending on the application, but may be, for example, 20% by mass or less, or 5% by mass or less.

[0199] <Method for producing a dispersion> One aspect of the present invention provides a method for producing the dispersion of the present disclosure. In one embodiment, the dispersion may be obtained by mixing organo-modified silicone (α) with a liquid medium. In one embodiment, the method for producing the dispersion includes a mixing step of mixing an emulsion containing an organo-modified silicone (α) with a hydrophobic polymer (β). In one embodiment, the method for producing the dispersion includes a polymerization step of polymerizing monomer components that are raw materials for a hydrophobic polymer (β) in the presence of an organo-modified silicone (α) (for example, in the presence of an emulsion containing an organo-modified silicone (α)) to obtain a dispersion.

[0200] An emulsion containing organo-modified silicone (α) may contain organo-modified silicone (α), a dispersion aid, and a liquid medium. The content of organo-modified silicone (α) in the emulsion is preferably 1% by mass or more, or 5% by mass or more, or 15% by mass or more, and preferably 70% by mass or less, or 50% by mass or less, or 30% by mass or less. In one embodiment, an emulsion containing organo-modified silicone (α) can be used as the dispersion in this embodiment.

[0201] <Uses of dispersions> Applications of the dispersion in this embodiment include various treatment agents such as surface treatment agents, water repellents, oil repellents, water- and oil-repellent agents, antifouling agents, stain removers, release agents, mold release agents, and the like.

[0202] ≪Method for Manufacturing Textile Products≫ One aspect of the present invention provides a textile product treated with the dispersion of the present disclosure (more specifically, a product obtained by treating fibers with the dispersion of the present disclosure). One aspect of the present invention also provides a method for producing a textile product, comprising the step of treating a substrate (more specifically, a fiber) with a dispersion of the present disclosure.

[0203] <Base material> Examples of substrates treated with the dispersion of this disclosure include various fibrous structures (for example, fabrics, paper, etc., which are used as filters, electrodes, supports, etc.), stone materials, and the like. The fibers included in the fibrous structure include: natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic or regenerated fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; and mixed fibers thereof (e.g., interwoven blended yarns). The fabric may be woven, knitted, or nonwoven. The base material may be fibers, yarns, or intermediate fiber products before they are made into fabric (e.g., sliver or roving yarn). The dispersion of this embodiment is particularly suitable for imparting water-repellent and / or oil-repellent properties to synthetic fibers.

[0204] Examples of natural fibers include cellulose fibers such as cotton, flax, and pulp, as well as chitin, chitosan, wool, and silk. Pulp may be wood pulp, for example. Specific examples of wood pulp include mechanical pulps such as groundwood pulp (GP), pressured groundwood pulp (PGW), and thermomechanical pulp (TMP); chemical pulps such as high-yield unbleached softwood kraft pulp (HNKP; N material), bleached softwood kraft pulp (NBKP; N material, NB material), unbleached hardwood kraft pulp (LUKP; L material), and bleached hardwood kraft pulp (LBKP; L material); recycled paper pulps such as dainking pulp (DIP) and waste pulp (WP); and semi-chemical pulp (CP).

[0205] Examples of synthetic fibers include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and copolymerized polyester; polyolefins such as linear low-density polyethylene, low-density polyethylene, high-density polyethylene, and polypropylene; polyamides such as nylon 6, nylon 66, nylon 610, and nylon 46; acrylic fibers such as polyacrylonitrile; and polyvinyl alcohol, polyurethane, and polyvinyl chloride. Examples of semi-synthetic fibers include acetate and triacetate. Examples of regenerated fibers include rayon, cupro, polynosic rayon, lyocell, and Tencel. Examples of inorganic fibers include glass fiber and carbon fiber.

[0206] The base material may be leather. In order to make the leather water-repellent and / or oil-repellent, the dispersion may be applied to the leather, for example, as an aqueous emulsion, at various stages of leather processing, for example, at the wetting stage of the leather or at the finishing stage of the leather.

[0207] The base material may be paper. The dispersion may be applied to a pre-formed paper product, or it may be applied at various stages of papermaking, for example, at the paper drying stage. Examples of paper products include paper made from bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked recycled paper, paper containers, molded bodies made of paper, etc. Specific examples of paper products include food packaging paper, gypsum board base paper, coated base paper, medium-grade paper, general liner, core, neutral pure white roll paper, neutral liner, rust-preventive liner, metal lamination paper, kraft paper, neutral printing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, neutral information paper, molded paper (molded containers), etc.

[0208] For example, when using woven or knitted fabrics (hereinafter also referred to as woven or knitted fabrics), after weaving or knitting the fibers to obtain a raw fabric, the raw fabric may be optionally post-processed to obtain a base material. The raw fabric may be obtained using a known loom or knitting machine. Conventional known pre-processing and / or post-processing may be performed during weaving or knitting. Examples of post-processing include scouring and relaxing. For example, the raw fabric may be scouring and relaxed at 80°C to 130°C, in a continuous or batch manner. Scouring and relaxing at 100°C or below in a batch manner is preferred, and the use of a high-pressure liquid-flow dyeing machine equipped with a jet nozzle is particularly preferred. After scouring and relaxing, the woven or knitted fabric may be pre-set. Pre-setting may be a dry heat treatment using a pin tenter, for example, at 170°C to 200°C for 30 to 120 seconds. After pre-setting, dyeing may be performed according to a conventionally known procedure, and then final setting may be performed as needed. A base material can be obtained by the above procedure.

[0209] <Treatment of substrate with dispersion> A textile product can be obtained by treating a substrate with the dispersion of this embodiment. "Treatment" here refers to applying the dispersion to the substrate by immersion, spraying, coating, etc. The dispersion may be applied to the substrate as is, or in the form of a treatment solution, which is a combination of the dispersion with other components (e.g., additional liquid media, various additives, etc.). In such a treatment solution, the cyclic siloxane (γ) concentration is further reduced than in the dispersion, thus providing the same advantages as the dispersion of this embodiment. Through treatment, the polymer, which is the active ingredient of the dispersion, penetrates into the substrate and / or adheres to the surface of the substrate. The dispersion may be applied to the surface of the substrate by known methods such as immersion, spraying, or foam coating, and then dried. For example, the dispersion may be brought into contact with the substrate by methods such as padding, spraying, squirt coating, or slit coating. Alternatively, the dispersion may be applied to the substrate by cleaning methods, such as washing or dry cleaning. The substrate to which the dispersion has adhered may be subjected to dry heat treatment. The dry heat conditions may be, for example, 105°C to 190°C for 30 to 150 seconds. After dry heat treatment, the substrate may be subjected to calendering to further improve its water-repellent properties. The textile product comprises a base material and a dispersion-derived component that adheres to the surface and / or interior of the base material. The dispersion-derived component includes an organo-modified silicone (α) and may optionally further include a hydrophobic polymer (β) and / or a cyclic siloxane (γ).

[0210] The substrate treated with the dispersion may preferably be dried and cured by heating in order to exhibit water-repellent and oil-repellent properties. Curing may be performed by applying the dispersion together with a suitable crosslinking agent. The heating temperature may be, for example, 100°C to 200°C, or 100°C to 170°C, or 100°C to 120°C. With the dispersion of this embodiment, good performance can be obtained even with heating at low temperatures (for example, 100°C to 140°C). The heating time may be, for example, 5 seconds to 60 minutes, or 30 seconds to 3 minutes.

[0211] <Substrate pretreatment> The substrate may be pre-treated before being treated with the dispersion of this disclosure. Pre-treatment can impart excellent durability to the textile product after treatment with the dispersion. Examples of pre-treatment include: cationization treatment by reacting the substrate with a reactive quaternary ammonium salt; anionization treatment such as sulfonation, carboxylation, or phosphorylation; and post-anionization treatment such as acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, or polymer coating.

[0212] Any of the aforementioned substrates can be used as the substrate for pretreatment. From the viewpoint of improving the water repellency of the substrate after pretreatment, the substrate to be subjected to pretreatment is preferably a fiber containing polyamide and / or polyester, and in particular, nylon such as nylon 6, nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, polylactic acid, and mixed fibers containing these are preferred.

[0213] The pretreatment method is not limited, and conventionally known methods may be used. The pretreatment solution may be dispersed and diluted in an organic solvent and / or water as needed, and then applied to the substrate by known methods such as immersion, spraying, or foam coating, and dried. The pH, temperature, etc., of the pretreatment solution may be adjusted according to the desired degree of pretreatment.

[0214] Through such pretreatment, a substrate containing at least one functional group (hereinafter sometimes referred to as a "specific functional group") can be obtained, for example, by the following method. (1) A method for attaching a compound having a specific functional group to a substrate. For example, a substrate may be functionalized using a treatment agent containing a compound having a specific functional group (hereinafter referred to as a functionalizing treatment agent). As long as the treated substrate has a sufficient amount of the specific functional group, a portion of the compound may be chemically bonded to the substrate. (2) A method for directly preparing a substrate having a specific functional group.

[0215] A specific functional group is, for example, -SO3M 1(In the formula, M 1 It is a monovalent cation. ) A monovalent group represented by -COOM 2 (In the formula, M 2 A monovalent group represented by -OP(O)(OX) is a monovalent cation, and -OP(O)(OX) 1 )(OX 2 )(wherein, X 1 and X 2 M may be at least one selected from the group consisting of monovalent groups (each independently represented by a hydrogen atom or an alkyl group having 1 to 22 carbon atoms). 1 , and M 2 Each of these may be, for example, H, K, Na, or an ammonium ion which may have substituents. 1 , and X 2 For each of these, the number of carbon atoms when it is an alkyl group is preferably 1 to 22 or 4 to 12.

[0216] The above -SO3M 1 Examples of compounds having this compound include phenolic polymers. Examples of phenolic polymers include those with the following general formula: [ka] [In the formula, X 2 This is a hydrogen atom, -SO3M 3 (In the formula, M 3 (where represents a hydrogen atom or a monovalent cation), a hydroxyphenylsulfonyl group, or the following general formula: [ka] (In the formula, M 4 (This represents a hydrogen atom or a monovalent cation.) This represents a base represented by , where n is an integer between 3 and 500. Examples of compounds represented by this formula can be given. The weight percentage of SO3 in the above compound is preferably 0.5% or more, or 3% or more, or 5% or more, and preferably 40% or less, or 30% or less, or 20% or less. The above M 3 and M 4Each of these may be H, K, Na, or an ammonium ion which may have substituents. The compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid, or a formalin condensate of sulfonated bisphenol S, or a formalin condensate of phenolsulfonic acid and bisphenol S, or a formalin condensate of sulfonated bisphenol S and bisphenol S, or a formalin condensate of phenolsulfonic acid and phenol.

[0217] The above-COOM 2 Examples of compounds having this property include polycarboxylic acid polymers. Polycarboxylic acid polymers may be polymers obtained by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc., as monomers. In addition to the above monomers, monomers copolymerizable with the monomers may also be used. Examples of copolymerizable monomers include ethylene, vinyl monomers (vinyl chloride, vinyl acetate, etc.), acrylamide, acrylates, and methacrylates. Examples of acrylates and methacrylates include compounds having a hydrocarbon group with 1 to 3 carbon atoms that may have substituents such as hydroxyl groups (for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, etc.). These copolymerizable monomers may be used individually or in combination of two or more.

[0218] One method for producing polycarboxylic acid polymers involves adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and / or its salt (and optionally a monomer copolymerizable with the monomer) and heating the solution at 30°C to 150°C for 2 to 5 hours. An aqueous solvent, such as methanol, ethanol, isopropyl alcohol, or acetone, may be added to the aqueous solution of the above-mentioned monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; redox polymerization initiators, such as combinations of persulfates and sodium bisulfite; hydrogen peroxide; and water-soluble azo polymerization initiators. These radical polymerization initiators may be used individually or in combination of two or more. Furthermore, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization during radical polymerization. The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by neutralizing agents such as alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0219] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, in that it provides good water repellency to the resulting textile product.

[0220] The polycarboxylic acid polymer may be a commercially available product such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., trade name) or "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., trade name).

[0221] The above - OP(O)(OX 1 )(OX 2 Examples of compounds having the following general formula: [ka] [In the formula, X 1 and X2 This is synonymous with the above, X 3 This represents an alkyl group with 1 to 22 carbon atoms. Examples of phosphate ester compounds represented by [formula] include [formula]. Examples of the above-mentioned phosphate ester compounds include monophosphate esters in which the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms, diphosphate esters in which the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms, triester phosphates in which the alkyl ester portion is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof. From the viewpoint of water repellency of the resulting textile product, lauryl phosphate esters and decyl phosphate esters are particularly preferred.

[0222] The phosphate ester compound may be a commercially available product such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name).

[0223] The above-mentioned functionalizing agent may be used, for example, as an aqueous solution. Such a functionalizing solution may contain acids, alkalis, surfactants, chelating agents, etc., as needed. The functionalizing solution may further contain salts, for example, to effectively adsorb compounds having specific functional groups onto the substrate by salting-out effect. Examples of such salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate. The substrate may be subjected to a padding treatment, immersion treatment, spray treatment, or coating treatment using the functionalizing solution. For example, a padding treatment can be performed using a padding apparatus described in the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun, pp. 396-397) and Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd., pp. 256-260). For example, a coating treatment can be performed using a coating machine described in the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senryo-sha, pp. 473-477). For immersion treatment, one example is to use a batch-type dyeing machine as described in the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senjisha, pp. 196-247). Suitable dyeing machines include liquid-jet dyeing machines, air-jet dyeing machines, drum dyeing machines, winds dyeing machines, washer dyeing machines, and cheese dyeing machines. For spray treatment, one example is to use an air spray that atomizes the pretreatment solution with compressed air and sprays it, or an air spray with a liquid-pressure atomization system.

[0224] The concentration of the functionalization solution, the functionalization treatment conditions, and the heat treatment conditions after the functionalization treatment may be adjusted as appropriate depending on the purpose. For example, the immersion temperature of the functionalization solution may be 60°C to 130°C, and the immersion time may be 5 minutes to 60 minutes. It is preferable to adjust the pH of the functionalization solution to 3 to 5. pH adjusting agents such as acetic acid and malic acid may be used for pH adjustment. After the functionalization treatment, it is preferable to remove any excess of the compound having a specific functional group by washing with water or the like. By performing this removal sufficiently, it is possible to suppress the inhibition of the development of water repellency by treatment with the dispersion of this disclosure, and in addition, the texture of the resulting textile product will be good. If the functionalization solution contains a solvent such as water, it is preferable to dry the functionalized substrate to remove the solvent such as water. The drying method is not particularly limited and may be either a dry heat method or a wet heat method. The drying temperature and drying time are also not particularly limited and may be, for example, above room temperature and below 200°C, and from 10 seconds to several days. If necessary, after drying, a heat treatment at 100°C to 180°C for about 10 seconds to 5 minutes may be performed.

[0225] When the substrate is dyed, the functionalization treatment may be performed before dyeing or in the same bath as the dyeing. For example, when performing reductive soaping, it is preferable to perform the functionalization treatment after dyeing and reductive soaping in order to prevent compounds having specific functional groups attached to the substrate (e.g., phenolic polymer compounds) from falling off during soaping.

[0226] The amount of compound having a specific functional group attached to 100 parts by mass of the substrate after functionalization treatment is preferably 1.0 to 7.0 parts by mass. Such an attachment amount is preferable from the viewpoint of achieving a high level of both durable water repellency and texture.

[0227] In the method described in (2) above, an example of a substrate into which a specific functional group is introduced is a cationic dyeable polyester (CD-PET). From the viewpoint of good water repellency of the resulting textile product, the zeta potential of the surface of such a substrate is preferably -100mV to -0.1mV or -50mV to -1mV. The above zeta potential can be measured by a zeta potential / particle size measurement system (for example, Otsuka Electronics Co., Ltd., model number ELSZ-1000ZS).

[0228] <Formation of additional layers> The textile product may include an additional layer placed on the substrate, in addition to the substrate and the dispersion-derived components. In one embodiment, the present disclosure may be provided as a laminated fabric having a breathable waterproof layer on one side of the woven or knitted fabric. The breathable waterproof layer may be laminated directly to the woven or knitted fabric or via an adhesive layer. When the laminated fabric is used for clothing or the like, the woven or knitted fabric side (i.e., the side opposite to the breathable waterproof layer) may be positioned to be exposed to rainwater, etc. Such a laminated fabric has excellent water repellency and breathable waterproofness, and the breathable waterproof layer does not peel off even in harsh environments, making it suitable for outdoor use, such as uniforms, sportswear, and outdoor products.

[0229] The breathable waterproof layer may be a layer of resin having waterproof and breathable properties. The resin may be applied directly to the woven or knitted fabric, or laminated to one side of the woven or knitted fabric via an adhesive layer as described later. For example, when using a blended entangled yarn having fine protrusions due to loops or slack in the woven or knitted fabric, the protrusions become firmly entangled with the adhesive layer or the breathable waterproof layer, creating an anchoring effect that makes it even more difficult for the woven or knitted fabric and the breathable waterproof layer to separate. In ordinary woven or knitted fabrics (woven or knitted fabrics in which the above-mentioned protrusions are not sufficiently maintained on the surface), the anchoring effect tends not to develop well, and therefore the woven or knitted fabric and the breathable waterproof layer tend to separate easily.

[0230] Polyurethane resin is preferred as the main component of the resin constituting the breathable waterproof layer, and for example, it is preferable that polyurethane resin is contained in a proportion of 80% by mass or more. Polyurethane resin is generally suitable for forming a resin layer that has breathability and waterproofing properties. The polyurethane resin may be a reaction product of polyisocyanate and polyol, and conventionally known polyurethane resins can be used. The moisture-permeable waterproof layer may have, for example, a microporous structure or a non-porous structure. If it has a microporous structure, inorganic fine powder can be included in the moisture-permeable waterproof layer to ensure the desired moisture permeability. Examples of inorganic fine powder include silicon dioxide, aluminum dioxide, titanium dioxide, and the like. The average primary particle size of the inorganic fine powder is preferably about 7 to 40 nm. The inorganic fine powder content is preferably 3 to 50% by mass, and more preferably 5 to 50% by mass, relative to the total amount of the moisture-permeable waterproof layer.

[0231] The thickness of the breathable waterproof layer is preferably 5 μm or more, or 10 μm or more, and preferably 30 μm or less, from the viewpoint of balancing waterproofness and breathability, texture, and tear strength.

[0232] The laminated fabric may include an adhesive layer, and the woven or knitted fabric and the breathable waterproof layer may be laminated via the adhesive layer.

[0233] The adhesive constituting the adhesive layer should preferably be one that has excellent compatibility with the breathable waterproof layer. For example, when the resin constituting the breathable waterproof layer is mainly composed of polyurethane resin, a polyurethane-based adhesive is preferred. The polyurethane-based adhesive may be ether-based, ester-based, polycarbonate-based, etc., but from the viewpoint of breathability, an ether-based adhesive is preferred.

[0234] The adhesive layer may be formed over the entire surface of the woven or knitted fabric on the side where the moisture-permeable waterproof layer is formed, or it may be formed in a pattern from the viewpoint of moisture permeability, texture, etc. In either case, it is preferable that it is uniformly distributed throughout.

[0235] From the viewpoint of durability of the laminated fabric, the thickness of the adhesive layer is preferably 10 μm or more, or 20 μm or more. If the thickness of the adhesive layer exceeds 100 μm, further improvement in adhesion is not achieved even if the thickness is increased, so from the viewpoint of manufacturing cost, it is preferably 100 μm or less, or 80 μm or less.

[0236] The laminated fabric may further have a lining fabric on the side of the breathable waterproof layer opposite to the woven or knitted fabric side. When the lining fabric protects the breathable waterproof layer, the waterproofness (water pressure resistance) and strength are further improved.

[0237] Laminated fabrics can have excellent waterproofing properties. In one embodiment of a laminated fabric, the water level measured according to the water resistance test specified in JIS L 1092:2009 Method A (low water pressure method) is preferably 10,000 mm or more, or 15,000 mm or more, or 16,000 mm or more, or 20,000 mm or more. There is no particular limit to the upper limit of the water level, but in one embodiment it may be 50,000 mm or less, or 25,000 mm or less.

[0238] Laminated fabrics can have excellent moisture permeability. In one embodiment of a laminated fabric, the moisture permeability measured according to JIS L 1099:2012 B-1 method (potassium acetate method) is preferably 10,000 g / m². 2 • 24 hours or more, or 15,000 g / m² 2 • 24 hours or more, or 20,000 g / m² 2 • 24 hours or more. There are no particular restrictions on the upper limit of this moisture permeability, but in one embodiment, 40,000 g / m². 2 • Less than 24 hours, or 35,000 g / m² 2 It may be 24h·mm or less.

[0239] In laminated fabrics, delamination between the woven / knitted fabric and the breathable waterproof layer can be suppressed. In one embodiment of a laminated fabric, the peel strength between the woven / knitted fabric and the breathable waterproof layer, measured according to the method of JIS L 1089, may be, for example, 5 N / 2.54 cm or more, or 5 to 50 N / 2.54 cm, or 6 to 30 N / 2.54 cm, or 9 to 25 N / 2.54 cm. Methods for improving peel strength include using woven / knitted fabrics that have not undergone calendering, and providing an adhesive layer.

[0240] Examples of methods for manufacturing laminated fabrics include the following: "1" A method comprising the step of forming a breathable waterproof layer by applying a resin that constitutes the breathable waterproof layer to the surface of a woven or knitted fabric. "2" A method comprising the steps of forming an adhesive layer on a woven or knitted fabric or on a breathable waterproof layer, and bonding the woven or knitted fabric and the breathable waterproof layer via the adhesive layer. In woven or knitted fabrics used in laminated fabrics, it is preferable to maintain as many protrusions on the fabric surface as possible. For example, when calendering is applied to a woven or knitted fabric, the fine protrusions of the blended entangled yarns may be flattened, resulting in a flat surface that may not achieve a specific water droplet rolling angle. Furthermore, calendering may prevent the air-retaining layer from being sufficiently maintained, making it impossible to achieve the desired water repellency. Therefore, it is preferable to carefully consider the conditions for calendering. For example, conditions that do not excessively reduce the protrusions of the blended entangled yarns (e.g., a temperature of 130°C or higher and a linear pressure of 200 to 20000 N / cm) should be adopted. Calendering may also be performed without heating.

[0241] In the method described in "1" above, a coating method can be used as a method for applying the resin constituting the breathable waterproof layer to the surface of the woven or knitted fabric. In the coating method, a knife coater or a comma coater can be used. Furthermore, from the viewpoint of obtaining excellent breathability, it is preferable to obtain the breathable waterproof layer by a wet method.

[0242] In the method described in "2" above, a lamination method is one example of a method for forming an adhesive layer on a woven or knitted fabric or a breathable waterproof layer. In the lamination method, a method using a resin solution or a hot melt method can be used to form the adhesive layer. First, a resin composition for forming a breathable waterproof layer (for example, a resin composition containing resin and an organic solvent) is applied to the surface of a release agent (release paper, release cloth, or release film, etc.) while adjusting the thickness with a clearance, and then heat-treated to completely react and form a breathable waterproof layer (film). The release agent may be removed as appropriate after the breathable waterproof layer has been formed. Then, an adhesive layer is formed on the woven or knitted fabric or the breathable waterproof layer. For example, in the method using a resin solution, a two-component curing type polyurethane resin solution with a viscosity adjusted to the range of 500 to 5000 mPa·s may be applied to the entire surface or in a pattern. After drying, an adhesive layer is formed, and the woven or knitted fabric and the breathable waterproof layer may be bonded together via the adhesive layer and pressed together (for example, by heat pressing). On the other hand, in the case of hot melt adhesives, it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practical terms, it is more preferable to use one that melts in a temperature range of about 80 to 150°C. In this case, first, the hot melt resin is melted while considering the melting point and viscosity at the time of melting. Then, the melted resin is applied to the woven or knitted fabric or the breathable waterproof layer, and the adhesive layer is formed by curing while cooling at room temperature. After that, the woven or knitted fabric and the breathable waterproof layer may be bonded together via the adhesive layer and pressed together.

[0243] After forming a breathable waterproof layer, a lining fabric may be laminated on top of it using any conventionally known method. As described above, the textile product of this embodiment is obtained.

[0244] The textile products of this embodiment are suitably used for clothing (e.g., uniforms, menswear, womenswear, sportswear, etc.) and other applications. [Examples]

[0245] The present invention will be further described below with reference to examples, but the present invention is not limited in any way by these examples.

[0246] Examples 1-24, Comparative Examples 1-4 <Synthesis of organo-modified silicones> [Synthesis Example 1] (Synthesis of copolymers of dimethylsiloxane and methylhydrogensiloxane) Methylhydrogensiloxane was synthesized using hexamethyldisiloxane (available from Tokyo Chemical Industry Co., Ltd.), methylhydrogensiloxane (available from Shin-Etsu Chemical Co., Ltd., Momentive, etc.), octamethylcyclotetrasiloxane (available from Tokyo Chemical Industry Co., Ltd.), and sulfuric acid. Methylhydrogensiloxane (Si-H: 0.5 mol) was charged into a three-necked flask, sulfuric acid was added, and while flowing nitrogen gas, octamethylcyclotetrasiloxane Si-Me: 0.44 mol and hexamethyldisiloxane Si-Me: 0.06 mol were charged, the temperature was raised to 80°C, and the reaction was carried out for 7 hours. After that, the mixture was removed by distillation under reduced pressure until the total concentration of D4 / D5 / D6 siloxanes reached the predetermined concentration shown in Table 1. D4 is octamethylcyclotetrasiloxane, D5 is decamethylcyclopentasiloxane, and D6 is dodecamethylcyclohexasiloxane. The concentrations of D4 / D5 / D6 siloxanes were confirmed using GC / MS (gas chromatograph-mass spectrometer) (Agilent Technologies, Inc., model numbers 7697A, 7890A, 5975C). Based on these results, the target copolymer of dimethylsiloxane and methylhydrogensiloxane (H-silicone 3) was obtained. 1 Measurements using a 1H NMR (nuclear magnetic resonance spectrometer) (JEOL, model ECZ500R) confirmed that the above H silicone 3 has a SiH:SiCH3 molar ratio of 5:5.

[0247] (Addition reaction) The H-silicone 3 obtained above, and a mixed solution of platinum(IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst, were placed in a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The flask was purged with nitrogen, and 1 equivalent of 1-octene was added dropwise to the mixture in the flask for every 1 equivalent of the Si-H reactive group of H-silicone 3. The inside of the vessel was heated to 120°C, and the addition reaction was carried out for 6 hours. The completion of the addition reaction was confirmed by FT-IR (Fourier transform infrared spectroscopy) analysis (Thermo Fisher Scientific, model NICOLET is20) of the obtained organo-modified silicone, and by confirming that the absorption spectrum originating from the SiH group of H-silicone 3 had disappeared. (In general formula (1), R 20 ,R 21 ,R 22 =CH3,R 23 =C8H 17 a:b=5:5, R 30 ~R 35 (=Equivalent to CH3) The amount of cyclic siloxane (γ) represented by general formula (1a) was confirmed by GC / MS. This confirmed that the only cyclic siloxane (γ) in the organo-modified silicone was D4 / D5 / D6 siloxane, and therefore the total amount of D4 / D5 / D6 siloxane was considered to be the amount of cyclic siloxane (γ).

[0248] [Synthesis Examples 2-17] Using the combinations of copolymers of dimethylsiloxane and methylhydrogensiloxane, and α-olefins listed in Tables 1 and 2, α-olefins were added in an amount equal to 1 equivalent for each methylhydrogen silicone's reactive group SiH, and organo-modified silicones were synthesized in the same manner as in Synthesis Example 1.

[0249] <Preparation of organo-modified silicone emulsion> 20 g of organo-modified silicone obtained in the above synthesis example, 3 g of sorbitan fatty acid ester (available from Kao Corporation, HLB 7 or less), 4.5 g of polyoxyethylene alkyl ether (available from Daiichi Kogyo Co., Ltd., HLB 8-14), and 0.75 g of cationic emulsifier (Lipoguard T-28, available from Kao Corporation) were charged and mixed until homogeneous by heating. After homogenization, 71.75 g of water was added and the mixture was emulsified and dispersed using ultrasound for 10 minutes to obtain an organo-modified silicone emulsion (organo-modified silicone content: 20% by mass).

[0250] <Synthesis of acrylic polymers> <Acrylic polymer 1> In an autoclave, 30.0 g of stearyl acrylate, 0.2 g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3 g of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 g of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4 g of alkyl(C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed and mixed and stirred at 45°C to obtain a mixture. This mixture was irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere to obtain an acrylic polymer emulsion (acrylic polymer 1) containing 30.0% by mass of the acrylic polymer.

[0251] <Acrylic polymer 2> In an autoclave, 16.0 g of stearyl acrylate, 3.2 g of behenyl acrylate, 4.8 g of stearyl methacrylate, 0.2 g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3 g of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 g of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4 g of alkyl(C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed and mixed and stirred at 45°C to obtain a mixture. This mixture was irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and under a nitrogen atmosphere, 6.0 g of vinyl chloride was continuously injected under pressure to maintain an autoclave internal pressure of 0.3 MPa, and radical polymerization was carried out at 60°C for 6 hours to obtain an acrylic polymer emulsion (acrylic polymer 2) containing 30.0% by mass of the acrylic polymer.

[0252] <Acrylic polymer 3> In an autoclave, 19.2g of stearyl acrylate, 4.2g of stearyl methacrylate, 0.6g of diacetone acrylamide, 0.2g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3g of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5g of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4g of alkyl(C16-18) trimethylammonium chloride, 12.5g of tripropylene glycol, and 54.8g of water were placed and mixed and stirred at 45°C to obtain a mixture. This mixture was then irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and under a nitrogen atmosphere, 6.0 g of vinylidene chloride was continuously injected under pressure to maintain an autoclave internal pressure of 0.3 MPa, and radical polymerization was carried out at 60°C for 6 hours to obtain an acrylic polymer emulsion (acrylic polymer 3) (pH=2.2) containing 30.0% by mass of the acrylic polymer.

[0253] <Acrylic polymer 4> In an autoclave, 22.5g of stearyl acrylate, 0.75g of Latemul PD-420, 0.75g of Latemul PD-430, 0.2g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3g of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5g of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4g of alkyl(C16-18) trimethylammonium chloride, 12.5g of tripropylene glycol, and 54.8g of water were placed and mixed and stirred at 45°C to obtain a mixture. This mixture was irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and radical polymerization was carried out at 60°C for 6 hours under a nitrogen atmosphere to obtain an acrylic polymer emulsion (acrylic polymer 4) (pH=2.1) containing 30.0% by mass of the acrylic polymer.

[0254] <Acrylic polymer 5> 3.3 g of triethanolamine, 3.3 g of RHODAFAC ASI 80, and 3.3 g of water were dissolved while cooling until homogeneous. This solution was mixed with 0.1 g of 990 acrylic polymer 4 (pH=2.1) to obtain an acrylic polymer emulsion (acrylic polymer 5) (pH=3.5) containing 29.7% by mass of the acrylic polymer.

[0255] <Acrylic polymer 6> 3.3 g of triethanolamine, 3.3 g of RHODAFAC ASI 80, and 3.3 g of water were dissolved while cooling until homogeneous. This solution was mixed with 0.1 g of 990 acrylic polymer 3 (pH=2.2) to obtain an acrylic polymer emulsion (acrylic polymer 6) (pH=3.5) containing 29.7% by mass of the acrylic polymer.

[0256] <Synthesis of urethane polymers> (Example of urethane polymer synthesis 1) 206.74 g of ditrimethylolpropane, 469.87 g of stearic acid, and 3.4 g of p-toluenesulfonic acid were placed in a 1000 ml flask. The mixture was heated to 140°C under a nitrogen atmosphere, and then dehydration was carried out at 140-190°C for 5 hours under a nitrogen stream at a heating rate of approximately 0.4°C / min. The nitrogen flow rate was 5 ml / min. After the reaction was complete, the acid value of the synthesized product was measured. The acid value was 2.0 mg KOH / g.

[0257] Next, 101.12 g of the above reaction mixture was placed in a 300 ml flask, and 23.78 g of hexamethylene diisocyanate, 25 g of methyl ethyl ketone, and 0.125 g of bismuth-based catalyst (Neostan U-600: manufactured by Nitto Kasei Co., Ltd.) were added. The reaction was carried out at 80°C for 7 hours. The reaction was continued until the NCO% reached 0.64%. After the reaction, the temperature was lowered to 40°C, and then 2.36 g of 3,5-dimethylpyrazole was added and the reaction was carried out at 40°C for 1 hour to obtain a urethane polymer. The weight-average molecular weight (Mw) of the obtained urethane polymer was measured using gel permeation chromatography (HLC-8320GPC (TOSOH CORPORATION)), and it was found to be 11700.

[0258] The obtained urethane polymer is R in the above general formula (UI-1). U31 The residue obtained by removing four hydroxyl groups from ditrimethylolpropane, with d being 2, e being 2, and W being 2. 1 is an ester group, R U32 is a heptadecyl group, V 1 A polyfunctional compound in which is a hydroxyl group, and in the above general formula (II), R U33 This compound is obtained by reacting a hexylene group with an isocyanate compound in which f is 2, and then blocking the unreacted isocyanate group with 3,5-dimethylpyrazole.

[0259] In a 500 mL stainless steel container, 120 g of the obtained urethane polymer, 50 g of methyl ethyl ketone, 5 g of Decagrin 1-L (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), 5 g of Decagrin 1-SV (nonionic surfactant, manufactured by Daiichi Kogyo Seiyaku), and 5 g of Arcard T-28 (cationic surfactant, manufactured by Lion Specialty Chemicals) were placed and heated to 50°C to dissolve. Next, 215 g of hot water at 80°C was added, and the mixture was emulsified for 20 minutes while maintaining the temperature at 80°C using an ultrasonic emulsifier US-600E (Nippon Seiki Seisakusho Co., Ltd.). After cooling, a urethane polymer emulsion containing 30.0% by mass of the urethane polymer was obtained.

[0260] <Other polymers> Zelan R3 (available from Chemours)

[0261] <Additional ingredients> Crosslinking agent NK Assist NY-11 (manufactured by Nikka Chemical Co., Ltd.)

[0262] <Preparation of dispersion> Dispersions were obtained by mixing each component and water as the liquid medium at room temperature to obtain the compositions shown in Tables 4 and 5 (the amounts in the tables are based on mass%). Specifically, in the example shown in Table 4, an organo-modified silicone emulsion, a crosslinking agent, and water were mixed, and in the example shown in Table 5, an organo-modified silicone emulsion, a hydrophobic polymer emulsion, a crosslinking agent, and water were mixed.

[0263] Examples 25-29 <Synthesis of acrylic polymers: Internal polymerization> Monomeric components, which are raw materials for acrylic polymers, were polymerized in the presence of organo-modified silicone.

[0264] <Acrylic polymer 7> Except for adding the organo-modified silicone from Synthesis Example 2 during the mixing and stirring at 45°C during the preparation of acrylic polymer 4 to obtain a mixture, the procedure was the same as for the preparation of acrylic polymer 4 to obtain an emulsion (acrylic polymer 7) containing 27.5% by mass of acrylic polymer and an additional 2.5% by mass of organo-modified silicone.

[0265] <Acrylic polymer 8> Except for using the organo-modified silicone from Synthesis Example 4 instead of Synthesis Example 2, the procedure was the same as for the preparation of acrylic polymer 7 to obtain an emulsion (acrylic polymer 8) containing 27.5% by mass of acrylic polymer and an additional 2.5% by mass of organo-modified silicone.

[0266] <Acrylic polymer 9> In an autoclave, 12.8 g of stearyl acrylate, 2.6 g of stearyl methacrylate, 0.6 g of diacetone acrylamide, 0.2 g of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 1.3 g of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 g of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.4 g of alkyl(C16-18) trimethylammonium chloride, 12.5 g of tripropylene glycol, and 54.8 g of water were placed. Then, 10 g of organo-modified silicone from Synthesis Example 4 was added, and the mixture was stirred at 45°C to obtain a mixture. This mixture was irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixture, and under a nitrogen atmosphere, 4.0 g of vinylidene chloride was continuously injected under pressure to maintain an autoclave internal pressure of 0.3 MPa, and radical polymerization was carried out at 60°C for 6 hours to obtain an emulsion (acrylic polymer 9) containing 20.0% by mass of acrylic polymer and an additional 10.0% by mass of organo-modified silicone.

[0267] <Acrylic polymer 10> Except for using the organo-modified silicone from Synthesis Example 16 instead of Synthesis Example 2, the procedure was the same as for the preparation of acrylic polymer 7 to obtain an emulsion (acrylic polymer 10) containing 27.5% by mass of acrylic polymer and an additional 2.5% by mass of organo-modified silicone.

[0268] <Additional ingredients> Crosslinking agent NK Assist NY-11 (manufactured by Nikka Chemical Co., Ltd.)

[0269] <Preparation of dispersion> A dispersion was obtained by mixing each component and water as the liquid medium at room temperature to obtain the composition shown in Table 6 (the amounts in the table are based on mass%).

[0270] The method for calculating the concentration of cyclic siloxane in the dispersion is as follows: [Cyclic siloxane concentration (unit: mass ppm)] = [Total amount of D4 / D5 / D6 per 1g of organo-modified silicone (unit: g)] × [Mass ratio of organo-modified silicone in organo-modified silicone emulsion] × [Mass ratio of organo-modified silicone emulsion in dispersion] × 10 6

[0271] <Manufacturing of textile products> The following fabrics were used for treatment. • Polyester (PET) / Polyurethane (PU) blended fabric (polyester / polyurethane mass ratio = 85 / 15) • 100% Polyester (PET) woven fabric 100% Nylon (Ny) woven fabric 100% cotton woven fabric • Polyester / cotton blend fabric (polyester / cotton = 70 / 30) White 100% polyester tricot knit

[0272] Each of the above-mentioned fabrics to be treated was immersed in 100g of the dispersion according to each example and comparative example at atmospheric pressure and 20±5℃ for 30 seconds, and then heat-treated at 150℃ for 2 minutes to obtain textile products. The obtained textile products were subjected to the following evaluations.

[0273] <Evaluation of Textile Products> (Anti-wicking assessment) A textile product measuring 2.5 cm wide x 10 cm long (using white 100% polyester tricot knit as the treated fabric) was immersed in red-colored water (0.1% solution of Alizaline Rubinol 3GA) up to 1.0 cm from the bottom edge in the vertical direction, and observed for 2 hours. After 2 hours, the maximum distance (i.e., the highest point) from the bottom edge of the red-colored portion of the textile product was measured. A smaller value indicates superior anti-wicking performance.

[0274] (Initial water repellency of textile products) For textile products, the water repellency test (spray test) was conducted according to JIS L 1092 (2009) 7.2, with a shower water temperature of 20°C. The results were evaluated visually using the following grades. A "+" was added to the grade if the properties were slightly better, and a "-" was added if the properties were slightly worse. The results are shown in Tables 4 and 5. Water repellency: condition 5: The surface should be free from moisture and water droplets. 4: The surface is not wet, but shows signs of small water droplets adhering to it. 3: Showing small, individual droplet-like moisture on the surface. 2: Shows moisture on half of the surface, indicating that small, individual moisture particles penetrate the fabric. 1: Those showing moisture across the entire surface.

[0275] (Durable water repellency of textile products) The water repellency of textile products after being washed 20 times (L-20) according to method 103 of JIS L 0217 (1995) was evaluated using the same procedure as for the initial water repellency described above.

[0276] (Processing stability: Gum-up) A 1000g test solution was prepared by diluting the dispersion with water with a hardness of 16 so that the solid content concentration of the dispersion was 1.8% by mass, and placed in a tray that could be temperature-controlled to 40°C. A 20cm wide and 80cm long piece of fabric to be treated (100% polyester woven fabric) was placed in a loop on the mangle to allow for continuous processing, and continuous processing was performed for 1 hour at a mangle pressure of 0.4 MPa. After 1 hour, the amount of solid matter adhering to the mangle was observed visually and by touch and evaluated according to the following criteria. Excellent: No solid material precipitation whatsoever. Good: Only a very small amount of solid material has precipitated. Acceptable: Contains some solid material Defective: Contains a lot of solid material.

[0277] (Peel strength) (Peel strength of coatings on textile products) Tests were conducted in accordance with JIS K 6404-5 (1999). Using a textile product as the base fabric, a hot-melt adhesive tape (MELCO Tape, manufactured by Sun Chemical Co., Ltd.) was heat-bonded to the base fabric at 150°C for 1 minute using a heat-sealing device. The peel strength between the base fabric and the seam tape layers was measured using an Autograph (AG-IS, manufactured by Shimadzu Corporation). The gripping device was pulled at a speed of 100 mm / min, and the average stress was defined as the peel strength [N / inch].

[0278] (Chalk mark evaluation of textile products) The surface of textile products was scratched with a fingernail and visually evaluated on a 5-point scale as shown below. The results are shown in Tables 4 and 5. 5: Clear claw marks are visible. 4: Claw marks are visible. 3: Slight claw marks are visible. 2: Almost no claw marks were found. 1: No trace left at all

[0279] (hue) For textile products, the color difference ΔE*ab was calculated from the L*a*b* values ​​measured using a Minolta spectrophotometer CM-3700A Spectra Magic NX CM-S100W with a D65 light source, 10-degree field of view, and 100% UV under SCI measurement, and this was used as the hue value. A smaller color difference is considered better. Color difference formula: ΔE * ab=[(Ln * -L0 * ) 2 +(an * -a0 * ) 2 +(bn * -b0 * ) 2 ]1 / 2 L0 * a0 * , b0 * = Hue value of the reference fabric Ln * an * , bn * = Hue value of each test fabric

[0280] [Table 1]

[0281] [Table 2]

[0282] [Table 3]

[0283] [Table 4]

[0284] [Table 5]

[0285] [Table 6] [Industrial applicability]

[0286] The dispersion of the present invention can be suitably applied, for example, to the manufacture of textile products.

Claims

1. The following general formula (1): 【Chemistry 1】 [In formula (1), R 20 , R 21 and R 22 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms. R 23 This represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 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 6 to 50 carbon atoms and having an aromatic ring, or an alkyl group having 6 to 100 carbon atoms, and a represents a non-negative integer, b represents a non-negative integer, (a + b) is between 10 and 200, and if a is 2 or greater, there are multiple R values. 20 and R 21 These may be the same or different, and if b is 2 or more, there may be multiple R 22 and R 23 These may be the same or different. A dispersion containing an organo-modified silicone (α) represented by, The dispersion contains the following general formula (1a): 【Chemistry 2】 [In formula (1a), R 20 and R 21 Each of these independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a 1 [This is an integer less than or equal to 30.] A dispersion in which the amount of cyclic siloxane (γ) represented by is 1000 ppm by mass or less.

2. In the above general formula (1), R 23 The dispersion according to claim 1, wherein the group is a saturated hydrocarbon group having 6 to 50 carbon atoms.

3. The dispersion further contains a hydrophobic polymer (β), The dispersion according to claim 1, wherein the hydrophobic polymer is one or more selected from the group consisting of urethane polymers and acrylic polymers.

4. The aforementioned acrylic polymer is of the following general formula (A-1): 【Transformation 3】 [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and, R 2 This represents a monovalent hydrocarbon group having 12 or more carbon atoms, which may have substituents. The dispersion according to claim 3, having constituent units derived from monomer (A1) represented by

5. The dispersion according to claim 3 or 4, wherein the acrylic polymer further comprises constituent units derived from monomers (VC) selected from the group consisting of vinyl chloride and vinylidene chloride.

6. The aforementioned acrylic polymer is of the following general formula (A-2): 【Chemistry 4】 [In formula (A-2), R 11 represents a hydrogen atom or a methyl group, R 12 This represents a divalent hydrocarbon group with 1 to 6 carbon atoms. Z represents an ester group or an amide group. W is -CO-R 13 (In the formula, R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. ) Groups represented by -NH-CO-NH 2 The basis, or the following formula (A-3): 【Transformation 5】 [This represents the base represented by ] The dispersion according to claim 3 or 4, further comprising constituent units derived from the monomer (A-2) represented by .

7. The aforementioned acrylic polymer (B1) When HLB is between 7 and 18, the following general formula (I-1): 【Transformation 6】 [In formula (I-1), R 3 represents a hydrogen atom or a methyl group, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 This represents a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. Compounds represented by, (B2) When HLB is between 7 and 18, the following general formula (II-1): 【Transformation 7】 [In formula (II-1), R 4 Y represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. 2 This represents a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. Compounds represented by, and (B3) Compounds obtained by adding a C2-C4 alkylene oxide to an oil or fat having an HLB of 7-18, hydroxyl group and polymerizable unsaturated group. The dispersion according to claim 3 or 4, further comprising a constituent unit derived from a reactive activator (B) which is at least one selected from the group consisting of the following.

8. The urethane polymer comprises at least the following general formula (UI-1): R U31 [-W 1 -R U32 ] d [-V 1 ] e (UI-1) [In equation (I-1), d represents an integer greater than or equal to 1, e represents an integer greater than or equal to 2, and (d+e) is between 3 and 6, R U31 represents an organic group with (d+e) valence, W 1 R represents a divalent group which is an ester group, amide group, urethane group, or urea group. U32 represents a monovalent hydrocarbon group with 8 to 24 carbon atoms in a straight or branched chain, V 1 V represents a hydroxyl group, an amino group, or a carboxyl group. However, there are e V 1 Two or more of these are hydroxyl groups and / or amino groups. A structural unit derived from a polyfunctional compound represented by the following general formula (UII): R U33 [-NCO] f (UI) [In formula (II), R U33 [where f represents an f-valent organic group, and f represents an integer from 2 to 7.] The dispersion according to claim 3, comprising a hydrophobic compound having a structural unit derived from an isocyanate compound represented by .

9. A method for producing a dispersion according to claim 3, A method comprising a mixing step of mixing an emulsion containing the organo-modified silicone (α) with the hydrophobic polymer (β).

10. A method for producing a dispersion according to claim 3, A method comprising a polymerization step of polymerizing monomer components that are raw materials for the hydrophobic polymer (β) in the presence of the organo-modified silicone (α) to obtain a dispersion.

11. The method according to claim 10, wherein the polymerization step is carried out in the presence of an emulsion containing the organo-modified silicone (α).

12. A textile product treated with the dispersion described in claim 1.

13. A method for producing a textile product, comprising the step of treating a substrate with the dispersion liquid described in claim 1.

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