Method for producing water-repellent fiber product

Abstract

To provide a method for producing a fiber product exhibiting superior water repellency.SOLUTION: A method for producing a water-repellent fiber product comprises: bringing a polyester copolymer having an anionic group into contact with a fibrous material; and bringing a non-fluorine water-repellent component into contact with the fibrous material after contact with the polyester copolymer having an anionic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention discloses a method for producing a water-repellent textile. [Background technology]

[0002] Fluorine-based water repellents containing fluorine-containing groups are known. Treating textiles and other articles with these fluorine-based water repellents can impart excellent water repellency to the articles. Fluorine-based water repellents are generally produced by polymerizing or copolymerizing monomers containing fluoroalkyl groups. To achieve sufficient water repellency, the fluoroalkyl groups must be oriented properly. Typically, the fluoroalkyl group is attached to the article, followed by a heat treatment at temperatures exceeding 130°C. However, such heat treatment is undesirable from the perspective of energy conservation. Furthermore, fluoroalkyl group-containing monomers are not only expensive but also persistent, posing a significant environmental burden. For these reasons, technologies have been developed in recent years to impart excellent water repellency to textiles and other articles by treating the articles with non-fluorine-based water repellents that do not contain fluorine. For example, Patent Document 1 proposes a water repellent containing a specific non-fluorine polymer emulsified and dispersed therein, with the aim of imparting water repellency comparable to that of conventional fluorine-based water repellents. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-328624 Summary of the Invention [Problem to be solved by the invention]

[0004] However, even the conventional non-fluorinated water repellent agent described in Patent Document 1 is still insufficient in its ability to impart water repellency to textile products. Furthermore, water-repellent textile products are also required to have durability (durable water repellency) that makes them resistant to deterioration in water repellency due to outdoor use, washing, etc., and in this respect, the above-mentioned conventional non-fluorinated water repellents are still insufficient. [Means for solving the problem]

[0005] The present invention discloses the following aspects as means for solving the above problems. <Aspect 1> contacting a textile material with a polyester copolymer having anionic groups; and contacting the textile material with a non-fluorine-based water-repellent component after contacting with the polyester copolymer having an anionic group; A method for producing a water-repellent textile product, comprising: The polyester copolymer contains dicarboxylic acid units and diol units, the dicarboxylic acid units contain 5 mol % or more and 30 mol % or less of at least one of units derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, and units derived from a tricarboxylic acid, the diol units are derived from a diol having a molecular weight of 48 to 900, and The intramolecular content of the dicarboxylic acid unit in the polyester copolymer is 50% by mass or more and 75% by mass or less. A method for manufacturing water-repellent textile products. <Aspect 2> Contacting a polyester copolymer having an anionic group with a polyester-based fiber; and contacting the polyester fiber with a non-fluorine-based water-repellent component after contacting the polyester fiber with the polyester copolymer having an anionic group; A method for producing a water-repellent textile product, comprising: The method for contacting the polyester copolymer having an anionic group includes: Dyeing polyester fibers, The polyester fiber after the dyeing treatment is subjected to a soaping treatment in the same bath as the dyeing solution or in a separate bath; and subjecting the polyester fiber after the soaping treatment to one or both of a hot water washing treatment and a water washing treatment; Including, one or both of a soaping liquid used in the soaping treatment and a cleaning liquid used in the cleaning treatment contain the polyester copolymer having an anionic group; the polyester copolymer having an anionic group contains a dicarboxylic acid unit and a diol unit, the dicarboxylic acid units contain at least one of a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and a unit derived from a tricarboxylic acid in an amount of 5 mol % to 30 mol %; The diol unit is derived from a diol having a molecular weight of 48 or more and 900 or less, and the content ratio of the dicarboxylic acid unit in the molecule of the polyester copolymer having an anionic group is 50% by mass or more and 75% by mass or less; A method for manufacturing water-repellent textile products. <Aspect 3> A method for producing the water-repellent textile product according to aspect 2, comprising: The polyester fiber after the dyeing treatment is subjected to the soaping treatment in the same bath as the dyeing solution, the dyeing solution used in the dyeing treatment contains the polyester copolymer having an anionic group, and At least a part of the polyester copolymer having an anionic group contained in the dyeing solution is used as at least a part of the polyester copolymer having an anionic group contained in the soaping solution. A method for manufacturing water-repellent textile products. <Aspect 4> A method for producing the water-repellent textile product according to aspect 2 or 3, comprising: and performing a soaping treatment of the polyester fiber having an anionic group after the dyeing treatment in the same bath as the dyeing solution, using the anionic group; The soaping solution used in the soaping treatment is prepared by adding at least the polyester copolymer having an anionic group to the dyeing solution after the dyeing treatment. A method for manufacturing water-repellent textile products. <Aspect 5> The non-fluorine-based water-repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound. A method for producing the water-repellent textile product according to any one of aspects 1 to 4. [Effects of the Invention]

[0006] According to the manufacturing method of the present disclosure, it is possible to produce water-repellent textile products with excellent water repellency (initial water repellency and durable water repellency). It is believed that excellent water repellency can be imparted to textile materials by contacting them with a polyester copolymer having an anionic group and then with a non-fluorinated water-repellent component. Furthermore, according to the technology of the present disclosure, it is also possible to produce products with excellent friction fastness or mechanical stability. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, a method for producing a water-repellent textile product according to one embodiment will be described, but the method for producing a water-repellent textile product according to the present disclosure is not limited to this embodiment.

[0008] A method for producing a water-repellent textile product according to one embodiment includes contacting a textile material with a polyester copolymer having anionic groups (polymer P), and contacting the textile material with a non-fluorine-based water-repellent component after contacting the textile material with the polyester copolymer having anionic groups. In other words, the method for producing a water-repellent textile product according to one embodiment involves pretreating the textile material with the polyester copolymer having anionic groups, and then performing a water-repellent treatment with the non-fluorine-based water-repellent component.

[0009] 1. Pretreatment In one embodiment of the method for producing a water-repellent textile product, a textile material is brought into contact with a polyester copolymer (polymer P) having an anionic group as a pretreatment.

[0010] 1.1 Textile materials The type of fiber material is not particularly limited. The fiber material may be at least one selected from natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (e.g., nylon), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may be in any form, such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, and paper. In one embodiment of the water-repellent fiber product, the fiber material preferably contains polyamide and polyester as raw materials, from the viewpoint of achieving superior water repellency. In particular, the fiber material is preferably at least one selected from nylons such as nylon 6 and nylon 6,6; polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid; and blended fibers containing these.

[0011] 1.2 Pretreatment agent In one embodiment of the method for producing a water-repellent textile product, a polyester copolymer having anionic groups (polymer P) is brought into contact with the textile material. For example, a pretreatment agent containing a polyester copolymer having anionic groups is prepared, and the pretreatment agent is brought into contact with the textile material. The pretreatment agent contains polymer P and may optionally further contain components other than polymer P (other components).

[0012] 1.2.1 Polymer P The polymer P contains dicarboxylic acid units and diol units and can be obtained by, for example, transesterification or direct polymerization.

[0013] (dicarboxylic acid unit) The dicarboxylic acid units constituting polymer P contain at least one of units (units X) derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, and units (units Y) derived from a tricarboxylic acid, in an amount of 5 mol % to 30 mol %. In other words, the dicarboxylic acid units constituting polymer P contain a total of 5 mol % to 30 mol % of units X and / or units Y, with the remainder consisting of dicarboxylic acid units other than units X and units Y. The dicarboxylic acid units constituting polymer P preferably contain 5 mol % to 20 mol %, more preferably 5 mol % to 15 mol %, and even more preferably 5 mol % to 12 mol % of units X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group. Alternatively, the dicarboxylic acid units constituting polymer P preferably contain 8 mol % to 20 mol %, more preferably 10 mol % to 20 mol %, of units Y derived from a tricarboxylic acid. When the dicarboxylic acid units constituting the polymer P have units X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, excellent water repellency can be imparted by having the units X in the above range. The same applies to the case where the dicarboxylic acid units constituting the polymer P have units Y derived from a tricarboxylic acid. In one embodiment, the "anionic group" of polymer P includes or is one or more selected from the group consisting of a sulfonic acid group, a sulfonate group, a carboxylic acid group, and a carboxylate group. Polymer P may also include other anionic groups, such as one or more groups selected from the group consisting of a sulfate group, a sulfate group, a phosphate group, and a phosphate group. Of the anionic groups contained in the polymer P, the proportion of those contained in units other than the units X and Y may be 30 mol % or less, or may be 0 mol %, relative to 100 mol % of the total amount of anionic groups.

[0014] Incidentally, a "unit derived from a tricarboxylic acid" can be expressed as a "unit derived from a dicarboxylic acid having one additional carboxylic acid group or carboxylic acid salt group." That is, in the present application, exceptionally, a "unit derived from a tricarboxylic acid" is considered to be a type of "dicarboxylic acid unit." On the other hand, in the present application, a "unit derived from a polyvalent carboxylic acid having tetravalent or higher carboxylic acids" is not considered to be a "dicarboxylic acid unit."

[0015] The dicarboxylic acid units constituting the polymer P may be derived from either an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, but are preferably derived from an aromatic dicarboxylic acid. The aromatic dicarboxylic acid may be, for example, at least one selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, and p-hydroxybenzoic acid. In particular, when the dicarboxylic acid units constituting the polymer P contain units derived from one or both of terephthalic acid and isophthalic acid, better performance is likely to be obtained. The aliphatic dicarboxylic acid may be, for example, at least one selected from adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and succinic acid. These dicarboxylic acids may be acid anhydrides or ester derivatives with lower alcohols or glycols.

[0016] The dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group may be any of the above-mentioned dicarboxylic acids to which a sulfonic acid group and / or a sulfonate salt group is bonded. The sulfonate salt group may be, for example, a metal salt group such as a Li salt, a Na salt, a K salt, or a Mg salt, or an amine salt group such as ammonia or triethanolamine. In particular, an alkali metal salt group, especially a Na salt group, is preferred. The dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group may be, for example, at least one selected from sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, salts thereof, and ester derivatives thereof such as dimethyl ester, diethyl ester, and diphenyl ester.

[0017] The tricarboxylic acid (dicarboxylic acid having one or both of a carboxylic acid group and a carboxylate group) may be any of the above-mentioned dicarboxylic acids to which a carboxylic acid group and / or a carboxylate group is bonded. In one embodiment, such tricarboxylic acids are intended to be free of sulfonic acid groups and sulfonate groups. The carboxylate group may be, for example, a metal salt group such as a Li salt, a Na salt, a K salt, or a Mg salt, or an amine salt group such as ammonia or triethanolamine. In particular, an alkali metal salt group, especially a Na salt group, is preferred. The tricarboxylic acid (carboxylic acid group-containing dicarboxylic acid) may be at least one selected from, for example, trimellitic acid, trimesic acid, 1,2,3-benzenetricarboxylic acid, salts thereof, and ester derivatives thereof, such as dimethyl ester, diethyl ester, and diphenyl ester.

[0018] The dicarboxylic acid units constituting the polymer P may include, for example, units derived from a dicarboxylic acid p1 that does not have a sulfonic acid group or a sulfonate salt group and does not fall under the category of a tricarboxylic acid, and units derived from a dicarboxylic acid p2 that has one or both of a sulfonic acid group and a sulfonate salt group and does not fall under the category of a tricarboxylic acid. Alternatively, the dicarboxylic acid units constituting the polymer P may include, for example, units derived from a dicarboxylic acid p1 that does not have a sulfonic acid group or a sulfonate salt group and does not fall under the category of a tricarboxylic acid, and units derived from a tricarboxylic acid (a dicarboxylic acid having one or both of a carboxylic acid group and a carboxylic acid salt group) p3. The carbon skeletons of the dicarboxylic acid p1, the dicarboxylic acid p2, and the tricarboxylic acid p3 may be the same or different. The dicarboxylic acid units constituting the polymer P may include, for example, units derived from either or both of terephthalic acid and isophthalic acid as dicarboxylic acid p1, which does not have a sulfonic acid group or a sulfonate salt group and does not fall under the category of tricarboxylic acid, and may include units derived from sulfoisophthalic acid as dicarboxylic acid p2, which has a sulfonic acid group or a sulfonate salt group and does not fall under the category of tricarboxylic acid. Specific examples of tricarboxylic acid p3 are as described above.

[0019] The dicarboxylic acid unit constituting the polymer P may be, for example, a unit derived from a dicarboxylic acid having a molecular weight of 100 or more and 300 or less. The molecular weight may be 100 or more from the viewpoint of imparting good water repellency, and may be 300 or less from the viewpoint of water solubility of the polymer P.

[0020] (Polycarboxylic acid units other than dicarboxylic acid units) In addition to the dicarboxylic acids, polymer P may also contain, as structural units, units derived from tetracarboxylic to hexacarboxylic polycarboxylic acids such as tetracarboxylic acids, pentacarboxylic acids, and hexacarboxylic acids. In one embodiment, the molecular weight of the polycarboxylic acids other than the dicarboxylic acids may be 100 or more and 400 or less. In polymer P, the proportion of dicarboxylic acid units relative to all polycarboxylic acid units may be, for example, more than 50 mol%, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more. Furthermore, the proportion of polycarboxylic acid units other than dicarboxylic acid units relative to all polycarboxylic acid units may be, for example, less than 50 mol%, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 1 mol% or less.

[0021] (diol units) The diol units constituting the polymer P are derived from a diol having a molecular weight of 48 to 900. The molecular weight of the diol is preferably 60 to 600, more preferably 60 to 300, and even more preferably 60 to 200. If the molecular weight of the diol is too low, the polymer P may not be sufficiently water-soluble, which may result in poor stability in the bath. On the other hand, if the molecular weight is too high, the polymer P may become excessively water-soluble, which may adversely affect the water repellency. In the case of an aromatic diol, the polymer P may not be sufficiently water-soluble, which may result in poor stability in the bath. In one embodiment, the diol units can have no anionic groups.

[0022] The diol units constituting the polymer P may be derived from either an aliphatic diol or an aromatic diol, but are preferably derived from a diol containing an aliphatic moiety, particularly an aliphatic diol. Examples of aliphatic diols include alkylene glycols and polyalkylene glycols. The diol may be at least one selected from polyethylene glycol, ethylene glycol, alkylene glycols having 3 or more carbon atoms, neopentyl glycol, polypropylene glycol, Pluronic® surfactants (polymers having an ethylene oxide-propylene oxide copolymerization moiety), and ethylene oxide adducts of bisphenol A (diols having an aromatic moiety and an aliphatic moiety). Among these, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a molecular weight of 200 to 600, 1,4-butanediol, and neopentyl glycol are preferred.

[0023] (Polyhydroxy compound units other than diol units) In addition to the diols described above, polymer P may also contain, as structural units derived from hydroxy compounds, units derived from trivalent to hexavalent polyhydroxy compounds such as triols, tetraols, pentaols, and hexaols. In one embodiment, the molecular weight of the polyhydroxy compound other than the diol may be 48 or more and 900 or less. In polymer P, the proportion of diol units relative to all polyhydroxy compound units may be, for example, more than 50 mol%, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more. Furthermore, the proportion of polyhydroxy compound units other than diol units relative to all polyhydroxy compound units may be, for example, less than 50 mol%, 40 mol% or less, 30 mol% or less, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 1 mol% or less.

[0024] The polymer P may contain a diol having a molecular weight of more than 900 in addition to the above diols as a constituent unit derived from a hydroxy compound. In one embodiment, from the viewpoint of water repellency, the proportion of units derived from a hydroxy compound having a molecular weight of more than 900 among the hydroxy compound units of polymer P is preferably 5% by mass or less, and may be 0% by mass. If the proportion of diols having a molecular weight of more than 900 is too high, polymer P may become excessively water-soluble, which may adversely affect water repellency.

[0025] (Weight average molecular weight of polymer P) The weight-average molecular weight of polymer P is not particularly limited. When the dicarboxylic acid units constituting polymer P include units derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, the weight-average molecular weight of polymer P may be, for example, 2,000 to 80,000, or 5,000 to 70,000. When the dicarboxylic acid units constituting polymer P include units derived from a tricarboxylic acid, the weight-average molecular weight of polymer P may be, for example, 2,000 to 80,000, or 2,000 to 20,000. When the weight-average molecular weight of polymer P is within these ranges, the water repellency of textile products can be further improved. In this application, the "weight-average molecular weight" is measured by size exclusion chromatography using an HLC-8120 (manufactured by Tosoh Corporation) instrument and a TSK-GEL Super AWM-H (manufactured by Tosoh Corporation) column, using 10 mM LiBr-DMF as the mobile phase, and polystyrene as the standard substance.

[0026] (Intramolecular content ratio of dicarboxylic acid units in polymer P) The intramolecular content of dicarboxylic acid units in polymer P is 50% by mass or more and 75% by mass or less, preferably 55% by mass or more and 75% by mass or less, and more preferably 60% by mass or more and 75% by mass or less. If this ratio is too low or too high, it is difficult to obtain sufficient water repellency.

[0027] 1.2.2 Components other than polymers The pretreatment agent may contain components other than the polymer P. The components other than the polymer P may include water, an organic solvent, a surfactant, and the like.

[0028] The organic solvent may be, for example, an alcohol having 1 to 10 carbon atoms. Specifically, it may be at least one selected from methanol, ethanol, isopropyl alcohol, ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.

[0029] The surfactant is not particularly limited and may be a known surfactant, for example, at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0030] The anionic surfactant may be at least one selected from, for example, sulfate esters, phosphate esters, or salts thereof of alkylene oxide adducts of aliphatic alcohols (fatty alcohols having 1 to 22 carbon atoms); sulfate esters, phosphate esters, or salts thereof of polyalkylene glycols obtained from alkylene oxides having 2 to 4 carbon atoms; sulfate esters, phosphate esters, or salts thereof of alkylene oxide adducts of mono- or polystyrenated phenols; sulfate esters, phosphate esters, or salts thereof of alkylene oxide adducts of mono- or polystyrenated alkyl (alkyl group having 1 to 22 carbon atoms) phenols; alkyl (alkyl group having 8 to 22 carbon atoms) benzenesulfonic acids or salts thereof; alkyl (alkyl group having 8 to 22 carbon atoms) sulfonic acids or salts thereof; α-olefin sulfonic acids having 8 to 22 carbon atoms or salts thereof; and α-sulfofatty acid alkyl esters (α-sulfofatty acid having 8 to 22 carbon atoms, alkyl group having 1 to 12 carbon atoms) or salts thereof. The salt may be, for example, at least one selected from alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts.

[0031] The nonionic surfactant may be at least one selected from, for example, an alkylene oxide adduct of an aliphatic alcohol (the aliphatic alcohol has 1 to 22 carbon atoms) or a fatty acid ester thereof (the fatty acid has 8 to 24 carbon atoms); a polyalkylene glycol obtained from an alkylene oxide having 2 to 4 carbon atoms or a fatty acid ester thereof (the fatty acid has 8 to 24 carbon atoms); an alkylene oxide adduct of a mono- or polystyrenated phenol or a fatty acid ester thereof (the fatty acid has 8 to 24 carbon atoms); and a fatty acid (the fatty acid has 8 to 24 carbon atoms) ester of an alkylene oxide adduct of a mono- or polystyrenated alkylphenol (the alkyl group has 1 to 22 carbon atoms).

[0032] The cationic surfactant may be at least one quaternary ammonium surfactant selected from the group consisting of benzalkonium chloride; a reaction product of a trialkylamine having one or two long-chain alkyl groups with a quaternizing agent; a reaction product of an alkylene oxide adduct of a mono- or di-alkylamine with a quaternizing agent; and an alkylpyridinium salt. The long-chain alkyl group of the trialkylamine may have, for example, 6 to 24 carbon atoms, and the remaining alkyl group of the trialkylamine may have, for example, 1 to 5 carbon atoms. The alkyl group of the mono- or di-alkylamine may have, for example, 6 to 24 carbon atoms. The alkylene oxide may have, for example, 2 to 4 carbon atoms, and the number of moles of the alkylene oxide added may be, for example, 2 to 50. The quaternizing agent may be at least one selected from the group consisting of an alkyl halide having an alkyl group with 1 to 5 carbon atoms and a dialkyl sulfate having an alkyl group with 1 to 5 carbon atoms. The alkyl group of the alkylpyridinium salt may have, for example, 3 to 24 carbon atoms.

[0033] The amphoteric surfactant may be at least one selected from, for example, alkylamine oxides, alanines, imidazolinium betaines, amidobetaines, acetic acid betaine, etc. Specific examples include long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, fatty acid amidopropyl dimethylamino acetic acid betaine, etc.

[0034] 1.2.3 Polymer P content There are no particular limitations on the amount of polymer P contained in the pretreatment agent. For example, the ratio (mass proportion) of polymer P contained in the pretreatment agent may be 0.1 to 70 mass %, or 0.5 to 50 mass %.

[0035] 1.3 Contact method In one embodiment of the method for manufacturing a water-repellent textile product, the polymer P (pretreatment agent containing the polymer P) is brought into contact with the textile material (subject to be treated), thereby allowing the polymer P to adhere to the textile material. When the pretreatment agent contains water, it is preferable to dry the pretreatment agent after it has been applied to the textile material in order to remove the water. The method for bringing the polymer P (pretreatment agent containing the polymer P) into contact with the fiber material is not particularly limited. For example, continuous contact methods (continuous methods) include padding, spraying, and coating, while batch methods include immersion. In the continuous method, the fibrous material is continuously fed into an impregnation device (a device that can continuously contact the pretreatment agent with the fibrous material) filled with a pretreatment agent containing polymer P (or a further diluted pretreatment liquid), and after the fibrous material is impregnated with the pretreatment liquid, any unnecessary pretreatment liquid is removed. On the other hand, the batch method includes, for example, a step of immersing a textile material in a pretreatment liquid and a step of removing the solvent remaining in the treated textile material. In the continuous method, a padder, a kiss roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator, etc. can be preferably used, and the padder type is particularly preferred. The continuous method is preferably used when the fiber material is in the form of a fabric such as a woven fabric. The drying method is not particularly limited, and may be either a dry heat method or a wet heat method. The dryer is not particularly limited, and a spread dryer such as a hot flue or a tenter is preferred. Examples of the batch method include methods using batch dyeing machines such as cotton dyeing machines, cheese dyeing machines, beam dyeing machines, liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. The batch method is preferably employed when the fiber material is not in the form of a fabric, for example, when it is loose fiber, top, sliver, skein, tow, yarn, etc., or when it is not suitable for a continuous method, such as knitted fabric. As a drying method, a cheese dryer, a beam dryer, a hot air dryer such as a tumble dryer, a high frequency dryer, or the like can be used. The treatment conditions, such as the concentration and temperature of the treatment liquid when contacting with a treatment agent containing polymer P by continuous treatment or batch treatment, can be adjusted appropriately taking into account various conditions such as the purpose and performance. The drying temperature is not particularly limited, and may be, for example, dried for 10 seconds to several days at room temperature to 200° C. If necessary, after drying, the film may be heat-treated at a temperature of 100 to 180° C. for 10 seconds to 5 minutes.

[0036] The pretreatment agent can be added to at least one of the treatment solutions used in dyeing, soaping, and / or washing of textile materials, and brought into contact with the textile materials. Two or three of the dyeing solution, soaping solution, and washing solution may contain polymer P. From the viewpoint of minimizing color change in polyester dyed textile products, it is more preferable to add the pretreatment agent to the soaping solution and / or washing solution, particularly the soaping solution and washing solution. For example, a case where polyester fibers are used as the fiber material will be described.

[0037] 1.3.1 Dyeing process As a method for contacting the polymer P, a dye solution containing the polymer P is used during dyeing of polyester fibers.

[0038] 1.3.1.1 Polyester fibers The polyester fiber to be dyed may be any fiber containing polyester. The polyester fiber may be, for example, one or both of a polyester fiber made of at least one homopolymer selected from ethylene terephthalate, propylene terephthalate, trimethylene terephthalate, and butylene terephthalate, or a copolymer thereof; or at least one conjugate fiber selected from blends, interwovens, and interknits of polyester fiber with other synthetic fibers or natural fibers. The polyester fiber may be in the form of at least one selected from yarn, knitted fabric, woven fabric, and nonwoven fabric. It is preferable that the polyester fiber is scoured.

[0039] 1.3.1.2 Staining solution The dyeing solution may contain a polymer P. The dyeing solution may also contain components other than the polymer P in addition to the polymer P.

[0040] (Amount of polymer P contained in the dye solution) The amount of polymer P contained in the dye solution is not particularly limited, but is preferably 0.005 g / L or more and 10.0 g / L or less, more preferably 0.010 g / L or more and 3.0 g / L or less, and even more preferably 0.1 g / L or more and 2.5 g / L or less.

[0041] (components other than polymer P) Components other than the polymer P include water, an organic solvent, a surfactant, etc. The dye solution may also contain an acid for adjusting the pH, a chelating agent, etc. Details of the organic solvent, surfactant, etc. are as described above.

[0042] From the viewpoint of achieving better level dyeing ability and dyeing ability, the dye solution preferably contains at least one surfactant selected from the group consisting of anionic surfactants and nonionic surfactants.

[0043] The amount of surfactant etc. contained in the dye solution is not particularly limited. From the viewpoint of achieving better level dyeing and dyeing ability, the amount of surfactant contained in the dye solution is preferably 0.001 g / L or more and 25 g / L or less, and more preferably 0.015 g / L or more and 6.0 g / L or less.

[0044] 1.3.1.3 Other conditions for dyeing process Other conditions for the dyeing treatment are not particularly limited, and any conditions that allow the polyester fiber to be dyed with the dye solution are adopted. For example, the following conditions can be mentioned.

[0045] (liquor ratio in dyeing process) The liquor ratio of polyester fiber to dye solution varies depending on the desired performance, but may be, for example, 1:3 to 1:30 by mass, preferably 1:5 to 1:25, and more preferably 1:5 to 1:20.

[0046] (dye) Any dye can be used as long as it can dye polyester fibers. For example, disperse dyes are suitable. The amount of dye used can be selected appropriately. For example, it may be 0.001% owf or more and 20% owf or less.

[0047] (dyeing machinery) The dyeing machine used in the dyeing treatment is not particularly limited, and conventional machines can be used, such as jet dyeing machines, winch dyeing machines, jigger dyeing machines, beam dyeing machines, cheese dyeing machines, Obermeyer dyeing machines, and high-pressure jet dyeing machines.

[0048] (Dyeing temperature and dyeing time) The dyeing process is carried out by bringing the polyester fiber into contact with the dyeing solution using the dyeing machine. The dyeing temperature and dyeing time can be the same as those of the conventional dyeing process. For example, the dyeing solution is heated to about 40 to 60°C, and the temperature is gradually increased over a period of about 50 to 80 minutes, or about 30 to 50 minutes if quick dyeing is desired, and high-temperature treatment is carried out at 120 to 140°C (preferably 125 to 135°C) for about 0 to 90 minutes, preferably 30 to 60 minutes.

[0049] 1. 3.2 Soaping treatment As a method for contacting the polymer P, a method of soaping the polyester fiber after dyeing treatment in the same bath as the dyeing solution or in a separate bath can be mentioned.

[0050] 1.3.2.1 Soaping liquid The soaping solution may contain a polymer P. In addition to the polymer P, the soaping solution may also contain components other than the polymer P.

[0051] (Amount of polymer P contained in soaping solution) The amount of polymer P contained in the soaping solution is not particularly limited, but is preferably 0.005 g / L or more and 10.0 g / L or less, more preferably 0.010 g / L or more and 3.0 g / L or less, and even more preferably 0.1 g / L or more and 2.5 g / L or less.

[0052] (components other than polymer P) Components other than the polymer P include known components used in soaping treatments (alkali, reducing agent, etc.). The soaping solution may also contain water, an organic solvent, a surfactant, etc. These may be derived from the dyeing solution. Details of the organic solvent, surfactant, etc. are as described above. The soaping solution may also contain an acid for adjusting the pH, a chelating agent, etc.

[0053] The reducing agent may be, for example, at least one selected from hydrosulfite, sodium hydrosulfite, thiourea dioxide, and reducing sugars (D-glucose, D-xylose, etc.). In this case, the pH adjuster may be any alkaline substance, such as caustic soda or soda ash. When at least one selected from hydrosulfite, sodium hydrosulfite, thiourea dioxide, and reducing sugars is used as the reducing agent, the pH adjuster is preferably caustic soda from the viewpoint of soaping effect. Alternatively, when at least one selected from hydrosulfite, sodium hydrosulfite, and thiourea dioxide is used as the reducing agent, the pH adjuster may be soda ash from the same viewpoint.

[0054] The reducing agent may be, for example, at least one sulfinic acid selected from sodium hydroxymethanesulfinate or a salt thereof, and in this case, the pH adjuster may be any acidic substance such as acetic acid or formic acid.

[0055] The reducing agent is preferably at least one selected from hydrosulfite, sodium hydrosulfite, thiourea dioxide, and sodium hydroxymethanesulfinate, and more preferably at least one selected from hydrosulfite, sodium hydrosulfite, and thiourea dioxide. When such a reducing agent is combined with the polymer P, fastness is likely to be further improved.

[0056] 1.3.2.2 Other conditions for soaping treatment Other conditions for the soaping treatment are not particularly limited, and any conditions that allow the polyester fiber to be soaped with the soaping solution are adopted. For example, the following conditions can be mentioned.

[0057] (liquor ratio in soaping treatment) The liquor ratio of polyester fiber to soaping liquid varies depending on the desired performance, but may be, for example, 1:3 to 1:30 by mass, preferably 1:5 to 1:25, more preferably 1:5 to 1:20, and even more preferably 1:5 to 1:15.

[0058] (Soaping temperature and time) The soaping temperature may be the same as that used in general dyeing processes, i.e., in the range of 60 to 140°C. However, taking into consideration deterioration in the physical properties and texture of the textile product, the soaping temperature is preferably in the range of 70 to 100°C, more preferably 70 to 90°C. The soaping time may be, for example, 5 to 60 minutes. From the viewpoints of ensuring sufficient soaping and preventing deterioration in the physical properties of the textile product, 10 to 30 minutes is preferred.

[0059] 1.3.3 Separate bath treatment (two-bath, two-stage method) As an example of a method in which the dyeing treatment and the soaping treatment are carried out in separate baths (two baths) (two-bath, two-stage method), the following first method can be mentioned.

[0060] First type: After the dyeing process, the dyeing solution is discarded, a new soaping solution (soaping bath) is prepared, and the soaping process is carried out.

[0061] 1.3.4 Same-bath treatment (one-bath, two-stage method) A specific example of a form in which the dyeing treatment and soaping treatment are performed in the same bath (one bath), i.e., a form in which the dyeing treatment and soaping treatment are performed in a one-bath two-stage method, is a form in which, after the dyeing treatment, the entire dye solution is not drained, but some or all of the dye solution is left and components necessary for soaping are added to perform the soaping treatment. In this way, performing the dyeing treatment and soaping treatment in the same bath (one bath) can save water and reduce energy.

[0062] In the single-bath treatment, for example, 20% by volume to 100% by volume, 50% by volume to 100% by volume, 70% by volume to 100% by volume, or 90% by volume to 100% by volume of the dyeing solution may be used to prepare the soaping solution. If the dyeing solution is not drained after the dyeing treatment, 100% by volume of the dyeing solution will be used as the soaping solution.

[0063] Specific examples of the case where the dyeing treatment and the soaping treatment are carried out in the same bath (one bath) include the following second and third modes. In the manufacturing method of the present disclosure, even if the dye solution used in the dyeing treatment contains polymer P, as in the second mode described below, the dyeing treatment of polyester fibers with the dye solution is carried out appropriately.

[0064] Second form: A form in which the dyeing solution used in the dyeing treatment contains a polymer P, and at least a part of the polymer P contained in the dyeing solution is used as at least a part of the polymer P contained in the soaping solution. More specifically, for example, after dyeing treatment is performed with a dyeing solution containing polymer P, a pH adjuster, a reducing agent, etc. are added to the dyeing solution (dye bath) to prepare a soaping solution (soaping bath), and then a soaping treatment is performed.

[0065] Third form: A form in which a soaping solution is prepared by adding at least polymer P to a dye solution (dye bath) after a dyeing treatment, and then a soaping treatment is performed. More specifically, for example, a form in which a pH adjuster, a reducing agent, etc. are added together with polymer P to a dye solution (dye bath) after a dyeing treatment, and then a soaping solution (soaping bath) is prepared, and then a soaping treatment is performed.

[0066] In both the second and third embodiments, the timing for adding a pH adjuster, a reducing agent, etc. to the dyeing solution after the dyeing treatment is not particularly limited. In particular, it is preferable to add a pH adjuster, a reducing agent, etc. to the dyeing solution when the temperature is lowered after the dyeing treatment, or after the temperature is lowered to the temperature for the soaping treatment (preferably after the temperature is lowered to the temperature for the soaping treatment). The same applies to the timing when polymer P is added in the third embodiment. Note that in the second embodiment, after the dyeing treatment using a dyeing solution containing polymer P, further polymer P may or may not be added to the dyeing solution. In the second embodiment, when further polymer P is added to the dyeing solution after the dyeing treatment, the timing may be the same as above.

[0067] 1. 3.5 Cleaning treatment As a method for contacting the polymer P, the polyester fiber after the soaping treatment may be subjected to one or both of a hot water washing treatment and a water washing treatment. Here, the washing liquid used in the washing treatment may contain the above-mentioned polymer P. Furthermore, the washing liquid may contain components other than the polymer P in addition to the polymer P.

[0068] (Amount of polymer P contained in the cleaning solution) The amount of polymer P contained in the cleaning solution is not particularly limited, but is preferably 0.005 g / L or more and 10.0 g / L or less, more preferably 0.010 g / L or more and 3.0 g / L or less, and even more preferably 0.1 g / L or more and 2.5 g / L or less.

[0069] (components other than polymer P) The cleaning liquid may contain components other than the polymer P. Examples of the components other than the polymer P include known components (such as a pH adjuster) used in hot water washing and / or water washing.

[0070] (Other conditions for cleaning process) Other conditions for the washing treatment are not particularly limited, and conditions that allow the polyester fiber to be washed with hot water and / or water using the above-mentioned washing solution are adopted. For example, the following conditions can be mentioned.

[0071] (Bath ratio in cleaning process) The liquor ratio of polyester fibers to cleaning liquid varies depending on the desired performance, etc., but may be, for example, 1:3 to 1:30 by mass, preferably 1:5 to 1:25, more preferably 1:5 to 1:20, and even more preferably 1:5 to 1:15.

[0072] (Cleaning temperature and cleaning time) The temperature for the washing treatment may be a general treatment temperature, for example, in the range of 20 to 100° C., preferably in the range of 30 to 90° C. The time for the washing treatment may be, for example, 2 to 60 minutes. From the viewpoint of sufficient washing and improving the quality of the various physical properties of the textile product, 5 to 30 minutes is preferred.

[0073] 1.4 Supplementary Information In the above explanation, the "dicarboxylic acid units" constituting polymer P exceptionally include "units derived from tricarboxylic acids (units derived from dicarboxylic acids having one additional carboxylic acid group and / or one additional carboxylic acid salt group)." However, if "dicarboxylic acid units" and "units derived from tricarboxylic acids" are distinguished, polymer P of the present disclosure can also be expressed as one or both of polyester copolymer P1 and polyester copolymer P2 below. In other words, the technology of the present disclosure also has an aspect of being a method for producing a water-repellent textile product using one or both of polyester copolymer P1 and polyester copolymer P2 below.

[0074] (Polyester copolymer P1) The polyester copolymer P1 contains dicarboxylic acid units p1-1 and diol units p1-2, the dicarboxylic acid units p1-1 containing 5 mol % to 30 mol % of units derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, the diol units p1-2 being derived from a diol having a molecular weight of 48 to 900, and the intramolecular content of the dicarboxylic acid units p1-1 in the polyester copolymer P1 being 50 mass % to 75 mass %.

[0075] (Polyester copolymer P2) The polyester copolymer P2 contains dicarboxylic acid units p2-1, diol units p2-2, and tricarboxylic acid units p2-3, and the proportion of the tricarboxylic acid units p2-3 in the total of the dicarboxylic acid units p2-1 and the tricarboxylic acid units p2-3 is 5 mol % or more and 30 mol % or less. The diol units p2-2 are derived from a diol having a molecular weight of 48 to 900. The intramolecular content of the dicarboxylic acid units p2-1 and the tricarboxylic acid units p2-3 in the polyester copolymer P2 is 50 mass % or more and 75 mass % or less.

[0076] In the polyester copolymer P2, the dicarboxylic acid units p2-1 may or may not contain units X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group. The total proportion of units X and units Y derived from a tricarboxylic acid in the dicarboxylic acid units p2-1 may be 5 mol % or more and 30 mol % or less.

[0077] 2.Water-repellent treatment In one embodiment of the method for producing a water-repellent textile product, the textile material after the pretreatment (after contact with the polyester copolymer having an anionic group) is contacted with a non-fluorine-based water-repellent component. For example, a water-repellent treatment agent containing a non-fluorine-based water-repellent component is prepared, and the water-repellent treatment agent is contacted with the textile material.

[0078] 2.1 Water repellent treatment The water repellent treatment agent contains a non-fluorine-based water repellent component, and may further contain, optionally, components other than the non-fluorine-based water repellent component (other components).

[0079] 2.1.1 Non-fluorine-based water-repellent ingredients The non-fluorine-based water-repellent component may be, for example, at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound. From the viewpoint of durable water repellency, the non-fluorine-based water-repellent component is preferably one or both of an acrylic compound and a silicone compound, and more preferably a silicone compound.

[0080] (acrylic compounds) The acrylic compound has, for example, a structural unit derived from a (meth)acrylic acid ester monomer (hereinafter also referred to as "component (A1)") represented by the following general formula (A1). The acrylic compound may further have a structural unit derived from a compound (hereinafter also referred to as "component (A2)") represented by the following general formula (A2). In this application, "(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.

[0081] [ka] [In formula (A1), R 1 is hydrogen or a methyl group, and R 2 represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent.]

[0082] [ka] [In formula (A2), R 11 is hydrogen or a methyl group, and R 12 is a divalent hydrocarbon group having 1 to 6 carbon atoms, Z is an ester group or an amide group, and W is -CO-R 13 (R 13is a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by —NH—CO—NH2, or a group represented by the following formula (W1).

[0083] [ka]

[0084] The component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring structure. Among these, from the viewpoint of water repellency, linear groups are preferred, and linear alkyl groups are more preferred. In this case, the water repellency is more excellent. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, the substituent may be one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In the general formula (A-1) above, R 2 is preferably an unsubstituted hydrocarbon group. When it is an unsubstituted hydrocarbon group, it is possible to improve the initial water repellency and also to contribute to improving the durable water repellency.

[0085] The number of carbon atoms in the hydrocarbon group is preferably 12 to 24, and more preferably 12 to 22. When the number of carbon atoms is within this range, the water repellency and texture become particularly excellent. A particularly preferred hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

[0086] Examples of the component (A1) include at least one selected from 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.

[0087] The component (A1) may have at least one functional group that can react with a crosslinking agent and is selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. 2 When a portion of (A1) has a functional group capable of reacting with a crosslinking agent, the durable water repellency can be further improved. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. Furthermore, when the component (A1) has an amino group, the texture can be further improved.

[0088] The component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group in one molecule.

[0089] The component (A1) may be used alone or in combination of two or more.

[0090] In the above formula (A2), R 12 may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic ring structure.

[0091] In the above formula (A2), when 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 a group represented by the above formula (W1). When Z is an amide group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is -CO-R 13 Preferably, R is a group represented by13 It is preferable that the carbon number is 1 to 2.

[0092] The component (A2) is not particularly limited, but examples thereof include diacetone acrylamide, 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl], and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency, diacetone acrylamide and 2-methylpropenoate [2-(2-oxo-2-imidazolidinyl)ethyl]methacrylamide are preferred as the component (A2).

[0093] The component (A2) may be used alone or in combination of two or more.

[0094] Regarding the content ratio of the structural units derived from component (A1) and the structural units derived from component (A2) in the acrylic compound, the ratio (A1) / (A2) of the mass of the blended component (A1) to the mass of the blended component (A2) is preferably 100 / 0 to 70 / 30, more preferably 99.9 / 0.1 to 70 / 30, even more preferably 99.8 / 0.2 to 80 / 20, and particularly preferably 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, durable water repellency and water repellency are improved.

[0095] The total mass of the (A1) component and the (A2) component to be blended is preferably 60 to 100 mass%, more preferably 70 to 99 mass%, and even more preferably 80 to 98 mass%, based on the total amount of the monomer components constituting the acrylic compound.

[0096] From the viewpoint of peel strength, the acrylic compound preferably contains, in addition to the component (A1) and the optional component (A2), at least one monomer (A3) selected from vinyl chloride and vinylidene chloride (hereinafter also referred to as "component (A3)") as a monomer component.

[0097] From the viewpoint of maintaining the texture of the textile product, the component (A3) is preferably vinyl chloride.

[0098] The mass of the (A3) component is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, based on the total mass of the (A1) and (A2) components (100), from the viewpoints of water repellency, durable water repellency, and peel strength. The mass of the (A3) component is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, based on the total mass of the (A1) and (A2) components (100), from the viewpoints of water repellency, durable water repellency, and texture.

[0099] In order to improve emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization, the acrylic compound preferably contains, in addition to component (A1) and any component (A2), at least one reactive emulsifier (A4) (hereinafter also referred to as "component (A4)") as a monomer component. The reactive emulsifier (A4) is selected from the group consisting of compounds having an HLB value of 7 to 18 and represented by the following general formula (A4-1), compounds having an HLB value of 7 to 18 and represented by the following general formula (A4-2), and compounds (A4-3) having an HLB value of 7 to 18 and formed by adding an alkylene oxide having 2 to 4 carbon atoms to an oil or fat having a hydroxyl group and a polymerizable unsaturated group.

[0100] [ka] [In formula (A4-1), R 3 is hydrogen or a methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0101] [ka] [In formula (A4-2), R 4is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.

[0102] In this application, the term "reactive emulsifier" refers to an emulsifying dispersant having radical reactivity, i.e., a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.

[0103] The "HLB" of a reactive emulsifier refers to the HLB value calculated from the following formula using the Griffin method, where the ethyleneoxy group in the reactive emulsifier is considered to be a hydrophilic group and all other groups are considered to be lipophilic groups. The HLB of the reactive emulsifier may be 7.0 to 16.0, 7.0 to 15.5, 7.0 to 15.0, or 7.0 to 14.5. If the HLB is outside this range, the initial Bundesmann water repellency and the Bundesmann water repellency after abrasion tend to decrease. HLB = 20 × [(molecular weight of hydrophilic group contained in reactive emulsifier) / (molecular weight of reactive emulsifier)]

[0104] The HLB of the compounds (A4-1) to (A4-3) is 7 to 18, and from the viewpoint of emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic compound (hereinafter simply referred to as emulsion stability), it is preferably 9 to 15. Furthermore, from the viewpoint of the storage stability of the water repellent composition containing a non-fluorinated water repellent component, it is more preferable to use in combination two or more reactive emulsifiers (A4) having different HLBs within the above range.

[0105] In the above general formula (A4-1), R 3 is hydrogen or a methyl group, and is preferably a methyl group in terms of copolymerizability with component (A1) and / or component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of acrylic compounds. Y 1 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 1The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure.

[0106] The compound represented by the above general formula (A4-1) is preferably a compound represented by the following general formula (A4-1-1).

[0107] [ka] [In formula (A4-1-1), R 3 is hydrogen or a methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms, and m can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 80 is preferred. When m is 2 or more, m A 1 O may be the same or different.]

[0108] In the compound represented by the above general formula (A4-1-1), R 3 is hydrogen or a methyl group, and is preferably a methyl group in terms of copolymerizability with component (A1) and / or component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsion stability of acrylic compounds. A 1 O is an alkyleneoxy group having 2 to 4 carbon atoms. 1 The types and combinations of O and the number m can be appropriately selected so as to fall within the above HLB range. In terms of emulsion stability of the acrylic compound, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A 1 O may be the same or different. 1 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0109] The reactive emulsifier represented by the general formula (A4-1-1) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0110] In the above general formula (A4-2), R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group. Examples of the unsaturated hydrocarbon group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradecadienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of emulsion stability of acrylic compounds, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0111] Y 2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. 2 The type, combination, and number of alkyleneoxy groups in the above formula (1) can be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure. In terms of emulsion stability of the acrylic compound, the alkyleneoxy group is preferably an ethyleneoxy group.

[0112] The compound represented by the above general formula (A4-2) is preferably a compound represented by the following general formula (A4-2-1).

[0113] [ka] [In formula (A4-2-1), R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and A 2O is an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A 2 O may be the same or different.]

[0114] R in the compound represented by the above general formula (A4-2-1) 4 represents R in the above general formula (A4-2). 4 The same can be mentioned.

[0115] A 2 O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of acrylic compounds, A 2 The types and combinations of O and the number of n can be appropriately selected so as to fall within the above HLB range. 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and further preferably an integer of 8 to 14. When n is 2 or more, n A 2 O may be the same or different. 2 When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0116] The reactive emulsifier represented by the general formula (A4-2-1) can be synthesized, for example, by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group, but is not limited thereto. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.

[0117] Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells and are collectively known as cardanol.

[0118] Compound (A4-3) has an HLB value of 7 to 18 and is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. Examples of fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of acrylic compounds, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above-mentioned HLB range, and from the viewpoint of emulsion stability of acrylic compounds, 20 to 50 moles are more preferred, and 25 to 45 moles are even more preferred. Furthermore, when two or more types of alkylene oxides are used, they can have a block addition structure or a random addition structure.

[0119] Compound (A4-3) can be synthesized, for example, by adding an alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group, but is not limited thereto. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, using an alkali catalyst such as caustic soda or caustic potassium under pressure at 120 to 170°C.

[0120] The proportion of the monomer of the component (A4) in the acrylic compound is preferably 0.5 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 3 to 10 mass %, relative to the total amount of monomer components constituting the acrylic compound, from the viewpoint of improving water repellency and emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic compound.

[0121] In order to improve durable water repellency, the acrylic compound may contain, in addition to the component (A1) and any component (A2), at least one second (meth)acrylic acid ester monomer (A5) (hereinafter also referred to as "component A5") selected from the group consisting of a monomer represented by the following general formula (A5-1), a monomer represented by the following general formula (A5-2), a monomer represented by the following general formula (A5-3), and a monomer represented by the following general formula (A5-4) as a monomer component.

[0122] [ka] [In formula (A5-1), R 5 is hydrogen or a methyl group, and R 6 is a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group, provided that the number of (meth)acryloyloxy groups in the molecule is 2 or less.]

[0123] [ka] [In formula (A5-2), R 7 is hydrogen or a methyl group, and R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.]

[0124] [ka] [In formula (A5-3), R 9 is an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms.

[0125] [ka] [In formula (A5-4), R 10 represents hydrogen or a methyl group, p represents an integer of 2 or greater, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.

[0126] The monomer (A5-1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety. In terms of reactivity with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a textile product is treated with an acrylic compound containing the monomer (A5-1) having a group reactive with such a crosslinking agent, together with the crosslinking agent, the durable water repellency of the resulting textile product can be improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0127] The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, a linear and / or saturated hydrocarbon group is preferred in terms of improving durable water repellency.

[0128] Specific examples of the monomer (A5-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving durable water repellency. Dimethylaminoethyl (meth)acrylate is also preferred in terms of improving texture.

[0129] From the viewpoint of water repellency, the mass of the (A5-1) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to the total mass of the (A1) component and the (A2) component, 100. From the viewpoint of water repellency, the mass of the (A5-1) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to the total mass of the (A1) component and the (A2) component, 100.

[0130] The monomer (A5-2) is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester moiety. Examples of the cyclic hydrocarbon group include an isobornyl group, a cyclohexyl group, and a dicyclopentanyl group. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. Furthermore, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and if it is alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of the monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used alone or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred, in terms of improving durable water repellency.

[0131] From the viewpoint of water repellency, the mass of the (A5-2) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended. From the viewpoint of water repellency, the mass of the (A5-2) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended.

[0132] The monomer (A5-3) above is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms or a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the chain hydrocarbon group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred, in terms of improving durable water repellency.

[0133] From the viewpoint of water repellency, the mass of the (A5-3) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the (A1) and (A2) components. From the viewpoint of water repellency, the mass of the (A5-3) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the (A1) and (A2) components.

[0134] The monomer (A5-4) is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. In the general formula (A5-4), T is a (meth)acryloyloxy group, and a polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule is preferred. In formula (A5-4), the p Ts may be the same or different. Specific examples of the compound include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. These monomers may be used alone or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred in terms of improving durable water repellency.

[0135] From the viewpoint of water repellency, the mass of the blended (A5-4) component is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the blended (A1) and (A2) components. From the viewpoint of water repellency, the mass of the blended (A5-4) component is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the blended (A1) and (A2) components.

[0136] From the viewpoint of water repellency and texture, the total constituent ratio of the monomers of the component (A5) in the acrylic compound is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, relative to the total amount of the monomer components constituting the acrylic compound.

[0137] From the viewpoint of water repellency, the mass of the (A5) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended. From the viewpoint of water repellency, the mass of the (A5) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended.

[0138] In addition to the component (A1) and the optional component (A2), the acrylic compound may contain a monofunctional monomer (A6) copolymerizable with these (hereinafter also referred to as "component (A6)"), within a range that does not impair the effects of the present invention.

[0139] Examples of component (A6) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the above (A1), (A2), and (A5), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other fluorine-free vinyl monomers other than component (A3). Note that (meth)acrylic acid esters having a hydrocarbon group other than components (A1), (A2), and (A5) may have a substituent on the hydrocarbon group such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group, or may have a substituent other than a group reactive with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, ester bond, amide bond, urethane bond, or the like. Examples of (meth)acrylic acid esters other than components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Among these, (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting textile product against coatings.

[0140] From the viewpoint of water repellency, the mass of the (A6) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended. From the viewpoint of water repellency, the mass of the (A6) monomer to be blended is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less, per 100 parts by mass of the combined mass of the (A1) and (A2) components to be blended.

[0141] The acrylic compound preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, as this improves durable water repellency. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. The acrylic compound preferably has an amino group, as this improves texture.

[0142] The weight-average molecular weight of the acrylic compound is preferably 30,000 or more. When the weight-average molecular weight is 30,000 or more, water repellency tends to be further improved. Furthermore, the weight-average molecular weight of the acrylic compound is more preferably 50,000 or more. In this case, water repellency can be more fully exhibited. The upper limit of the weight-average molecular weight of the acrylic compound is preferably about 5,000,000.

[0143] The weight-average molecular weight of the acrylic compound is measured using a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation) at a column temperature of 40°C and a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent, and is expressed in terms of standard polystyrene. Three columns manufactured by Tosoh Corporation under the trade names TSK-GELG5000HHR, G4000HHR, and G3000HHR are used in this experiment.

[0144] The melt viscosity of the acrylic compound at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, good texture tends to be maintained. Furthermore, when the acrylic compound is emulsified or dispersed to form a water repellent composition, precipitation or sedimentation of the acrylic compound can be suppressed, and therefore good storage stability of the water repellent composition tends to be maintained. Furthermore, the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, sufficient water repellency is exhibited while the texture is also improved.

[0145] "Melt viscosity at 105°C" is determined by placing 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm) using an elevated flow tester (e.g., Shimadzu CFT-500), holding the temperature at 105°C for 6 minutes, and measuring the melt viscosity at 100 kgf / cm using a plunger. 2 This refers to the viscosity when measured under a load of 1000 kJ / cm.

[0146] (Silicone compounds) The silicone compound is, for example, at least one of a silicone resin and a silicone oil. Among these silicone compounds, silicone resin is preferred from the viewpoint of water repellency. The silicone compound may be used alone or in combination of two or more.

[0147] The silicone resin may be an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent, which is solid at 25°C and has a three-dimensional structure, where M, D, T, and Q are each (R'')SiO 0.5 Unit, (R'')2SiO unit, R''SiO 1.5 units and SiO2 units. R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0148] Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have moieties designated as MDQ, MTQ, or MDTQ.

[0149] Silicone resins can be obtained alone or as a solution in a suitable solvent, such as relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, or a mixture of these solvents.

[0150] Examples of silicone resin solutions include KF7312J (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane), KF7312F (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane), KF9021L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane), and KF7312L (a 50:50 (mass ratio) mixture of trimethylsilyl group-containing polysiloxane:low-viscosity methylpolysiloxane) commercially available from Shin-Etsu Chemical Co., Ltd.

[0151] Examples of silicone resins alone include MQ-1600 solid Resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 Flake Resin (a mixture of trimethylsilyl group-containing polysiloxane and polypropylsilsesquioxane), both of which are commercially available from Toray Dow Corning Co., Ltd. The above-mentioned commercially available products contain trimethylsilyl group-containing polysiloxane, and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0152] Silicone oil is linear organopolysiloxane, and can have organic group at least in either the side chain or end of organopolysiloxane.As this silicone oil, can use the same as hydrophobic silicone oil and functionalized silicone oil, for example, can list straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil; modified silicone oil such as amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher aliphatic amide-modified silicone oil.

[0153] Amino-modified silicone oils include compounds having an organic group containing an amino group and / or an imino group at at least one of the side chains and terminals of an organopolysiloxane. Examples of such organic groups include organic groups represented by -R-NH2 and organic groups represented by -R-NH-R'-NH2. Examples of R and R' include divalent groups such as ethylene and propylene. Some or all of the amino groups and / or imino groups may be blocked amino groups and / or imino groups. Blocked amino groups and / or imino groups can be obtained, for example, by treating the amino groups and / or imino groups with a blocking agent. Examples of blocking agents include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

[0154] From the viewpoint of water repellency, the functional group equivalent weight of the amino-modified silicone oil is preferably from 100 to 20,000 g / mol, more preferably from 150 to 12,000 g / mol, and even more preferably from 200 to 4,000 g / mol.

[0155] The amino-modified silicone oil is preferably liquid at 25° C. The kinematic viscosity of the amino-modified silicone oil at 25° C. is 10 to 100,000 mm 2 / s, and 10 to 30,000 mm 2 / s is more preferable, and 10 to 5,000 mm 2 More preferably, the kinematic viscosity at 25°C is 100,000 mm / s. 2 If the kinematic viscosity is greater than 1 / s, the viscosity will be too high and workability will tend to be poor. The kinematic viscosity at 25°C refers to the value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0156] Amino-modified silicone oils are readily available as commercially available products, such as KF8005, KF-868, KF-864, KF-393, and KF-8021 (all of which are trade names manufactured by Shin-Etsu Chemical Co., Ltd.), TSF-4709 and XF42-B1989 (all of which are trade names manufactured by Momentive Performance Materials Japan Co., Ltd.), BY16-872, SF-8417, BY16-853U, and BY16-892 (all of which are trade names manufactured by Dow Corning Toray Co., Ltd.), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and WACKER® FINISH WR 301 (manufactured by Wacker Asahi Kasei Silicones).

[0157] Silicone oils other than amino-modified silicone oils are also readily available as commercially available products. Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: carboxyl-modified silicone oil), SF8428 (manufactured by Dow Corning Toray Co., Ltd., trade name: carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil), and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil). , higher fatty acid ester modified silicone oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: dimethyl silicone oil), SF8416 (manufactured by Dow Corning Toray Co., Ltd., trade name: alkyl modified silicone oil), SH203 (manufactured by Dow Corning Toray Co., Ltd., trade name: alkyl aralkyl modified silicone oil), SF8410 (manufactured by Dow Corning Toray Co., Ltd., trade name: polyether modified silicone oil).

[0158] The silicone compound may be an organo-modified silicone represented by the following general formula (1): In the following general formula (1), the structural units may be arranged in blocks, randomly, or alternately.

[0159] [ka] [In formula (1), R 20 , R 21 and R 22 are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 is a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 40 carbon atoms, and R 30 , R 31 , R 32 , R 33 , R 34 and R 35are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 40 carbon atoms; a is an integer of 0 or more; b is an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, a plurality of R 20 and R 21 may be the same or different, and when b is 2 or more, there are multiple R 22 and R 23 may be the same or different.

[0160] In the organo-modified silicone, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. R 20 , R 21 and R 22 are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0161] Examples of the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms and a group represented by the following general formula (2) or (3).

[0162] [ka] [In formula (2), R 40 is an alkylene group having 2 to 6 carbon atoms, and R 41 is a single bond or an alkylene group having 1 to 4 carbon atoms, and c is an integer of 0 to 3. When c is 2 or 3, multiple R 41 may be the same or different.]

[0163] The alkylene group may be linear or branched.

[0164] [ka] [In formula (3), R 42 is an alkylene group having 2 to 6 carbon atoms, and R 43 is a single bond or an alkylene group having 1 to 4 carbon atoms, and d is an integer of 0 to 3. When d is 2 or 3, multiple R 43 may be the same or different.]

[0165] The alkylene group may be linear or branched.

[0166] Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

[0167] In the group represented by the general formula (2), R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0168] In the group represented by the general formula (3), R 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0169] As the hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, the aralkyl group having 8 to 40 carbon atoms and the group represented by general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the aralkyl group having 8 to 40 carbon atoms is more preferred in that it can improve water repellency.

[0170] The alkyl group having 3 to 40 carbon atoms may be linear or branched. Examples of the alkyl group having 3 to 40 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, behenyl, hexacosyl, octacosyl, triacontyl, and dotriacontyl. As the alkyl group having 3 to 40 carbon atoms, an alkyl group having 12 to 36 carbon atoms is preferred, and an alkyl group having 16 to 34 carbon atoms is more preferred, in terms of improving water repellency. The fewer the carbon atoms in the alkyl group, the better the chalk mark resistance. Furthermore, the greater the carbon number in the alkyl group, the better the water repellency. Furthermore, if the carbon number exceeds 40, the stability of the dispersion tends to decrease. Furthermore, if the carbon number is less than 3, the water repellency tends to be poor.

[0171] In organo-modified silicones, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 40 carbon atoms. R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0172] In the organo-modified silicone, a is an integer of equal to or greater than 0. In terms of ease of industrial production, availability, and superior peel strength, a is preferably equal to or less than 40, and more preferably equal to or less than 30.

[0173] In the organo-modified silicone, (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.

[0174] Organo-modified silicones can be synthesized by conventional methods, for example, by subjecting silicone having a SiH group to a hydrosilylation reaction with an aromatic compound and / or an α-olefin having a vinyl group.

[0175] Examples of the silicone having a SiH group include methylhydrogensilicone and a copolymer of dimethylsiloxane and methylhydrogensiloxane, each having a degree of polymerization of 10 to 200. Among these, methylhydrogensilicone is preferred because it is easy to produce industrially and is readily available.

[0176] The aromatic compound having a vinyl group is represented by the formula (1) R 23 In the above formula, the aromatic compound is a compound from which a hydrocarbon group having an aromatic ring and 8 to 40 carbon atoms is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0177] The above α-olefin is represented by R in the above general formula (1). 23In the above formula, it is a compound from which an alkyl group having 3 to 40 carbon atoms is derived. Examples of α-olefins include α-olefins having 3 to 40 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), and 1-dotriacontene (C32).

[0178] The hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the α-olefin in a stepwise or all at once, if necessary, in the presence of a catalyst.

[0179] The amounts of the SiH group-containing silicone, vinyl group-containing aromatic compound, and α-olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight or number average molecular weight of the SiH group-containing silicone, etc.

[0180] Examples of catalysts used in the hydrosilylation reaction include platinum and palladium compounds, with platinum compounds being preferred, such as platinum(IV) chloride.

[0181] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10 to 200° C., preferably 50 to 150° C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150° C.

[0182] The hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction proceeds without a solvent, but a solvent may also be used. Examples of the solvent include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0183] As the non-fluorine-based water-repellent component, from the viewpoints of water repellency and chalk mark prevention, it is preferable to use the above-mentioned acrylic compound and the above-mentioned silicone compound in combination. The mass ratio of the acrylic compound (α) to the silicone compound (β) is not particularly limited. For example, when the silicone compound (β) is a silicone resin, the silicone compound (β) may account for 1 to 99 parts by mass, assuming that the total of the acrylic compound (α) and the silicone compound (β) is 100 parts by mass. The ratio is preferably 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, and even more preferably 15 to 95 parts by mass. Having the ratio of the silicone compound (β) within this range results in excellent water repellency and Bundesmann water repellency after wear. Alternatively, when the silicone compound (β) is an organo-modified silicone, the silicone compound (β) may account for 10 to 90 parts by mass, assuming that the total of the acrylic compound (α) and the silicone compound (β) is 100 parts by mass. The amount is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass. When the proportion of the silicone compound (β) is within this range, the water repellency is excellent and chalk marks are less likely to occur.

[0184] (wax-based compounds) The wax-based compound is, for example, at least one selected from paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and vegetable wax, and mineral wax, and from the viewpoints of water repellency, durable water repellency, and texture, paraffin wax is preferred.

[0185] The wax-based compound may be, for example, one or both of a normal alkane and a normal alkene. From the viewpoints of water repellency, durable water repellency, and texture, the wax-based compound is preferably a normal alkane.

[0186] Examples of normal alkanes include at least one selected from tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane. From the viewpoints of water repellency, durable water repellency, and texture, the normal alkanes are preferably triacontane, hentriacontane, and dotriacontane.

[0187] Examples of normal alkenes include at least one selected from 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene. From the viewpoints of water repellency, durable water repellency, and texture, the normal alkene is preferably at least one selected from triacontene, hentriacontene, and dotriacontene.

[0188] The number of carbon atoms in the wax-based compound is not particularly limited, but may be 20 to 60, and is preferably 25 to 45 from the viewpoints of water repellency, durable water repellency, and texture.

[0189] The weight average molecular weight of the wax-based compound is not particularly limited, but may be 300 to 850, and is preferably 300 to 700 from the viewpoints of water repellency, durable water repellency and texture.

[0190] From the viewpoint of good water repellency and durable water repellency, particularly good water repellency and durable water repellency to cotton, the melting point of the wax-based compound is preferably 35 to 90° C., more preferably 40 to 85° C., even more preferably 45 to 80° C., and still more preferably 50 to 75° C. The melting point of the wax-based compound refers to a value measured by the same method as in JIS K2235-1991 6.3.

[0191] The penetration of the wax-based compound is not particularly limited, but may be, for example, 30 or less, and from the viewpoint of water repellency and durable water repellency, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The penetration of the wax-based compound is not particularly limited, but may be, for example, 0.1 or more, or 1 or more. The penetration of the wax-based compound refers to a value measured by the same method as JIS K2235-1991 6.4.

[0192] (urethane compounds) The urethane-based compound is, for example, a reaction product of an aliphatic polyisocyanate derivative, a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. More specifically, for example, (U1) an aliphatic polyisocyanate derivative having an average number of isocyanate groups of 2 or more; (U2) a long-chain active hydrogen compound having both a hydrocarbon group and an active hydrogen group having 12 to 30 carbon atoms; (U3) a cationic active hydrogen compound having both an active hydrogen group and a cationic group; (U4) an acid compound that forms a salt with a cationic group; The urethane-based compound may be a reaction product of the above. Here, the concentration of the hydrocarbon group may be 30% or more and 85% or less. The aliphatic polyisocyanate derivative may also contain an isocyanurate derivative of an aliphatic polyisocyanate. Furthermore, in the cationic active hydrogen compound, the cationic group may be a tertiary amino group, the active hydrogen group may be a hydroxyl group, and the cationic active hydrogen compound may have two or more hydroxyl groups per molecule. When the urethane-based compound is a reaction product obtained using a long-chain active hydrogen compound and the concentration of the hydrocarbon group is a predetermined ratio, the compound is likely to have excellent water repellency. When the urethane-based compound is a reaction product obtained using a cationic active hydrogen compound, for example, affinity with fibers is improved, which tends to improve washing durability.

[0193] Examples of the aliphatic polyisocyanate constituting the aliphatic polyisocyanate derivative (U1) include aliphatic diisocyanates such as hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, etc. In the present application, the term "aliphatic polyisocyanate" is a concept that includes alicyclic polyisocyanates.

[0194] Examples of alicyclic polyisocyanates include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-, or 2,2'-methylenebis(cyclohexyl isocyanate) or a mixture thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0195] The aliphatic polyisocyanate is preferably one or both of hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter simply referred to as bis(isocyanatomethyl)cyclohexane), and more preferably hexamethylene diisocyanate.

[0196] Examples of the aliphatic polyisocyanate derivatives include polymers of the above-mentioned aliphatic polyisocyanates (for example, dimers, trimers (for example, isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (for example, allophanate derivatives produced by reacting the above-mentioned aliphatic polyisocyanates with monohydric alcohols or dihydric alcohols), polyol derivatives (for example, polyol derivatives (alcohol adducts, preferably trimethylolpropane) produced by reacting the above-mentioned aliphatic polyisocyanates with trihydric alcohols (for example, trimethylolpropane, etc.)), and Pan adducts), biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanates with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the above-mentioned aliphatic polyisocyanates with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned aliphatic polyisocyanates), uretdione derivatives, uretonimine derivatives, etc.

[0197] The aliphatic polyisocyanate derivative is preferably at least one of an isocyanurate derivative, a trimethylolpropane adduct, an allophanate derivative, and a biuret derivative, and more preferably an isocyanurate derivative. When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture becomes good.

[0198] The aliphatic polyisocyanate derivative is more preferably at least one of an isocyanurate derivative of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, a biuret derivative of hexamethylene diisocyanate, and an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, and even more preferably an isocyanurate derivative of hexamethylene diisocyanate.

[0199] The aliphatic polyisocyanate derivatives can be used alone or in combination of two or more. Preferred examples include the use of an isocyanurate derivative of hexamethylene diisocyanate alone, or the use of an isocyanurate derivative of hexamethylene diisocyanate in combination with at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. In this case, the blending ratio of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more relative to 100 parts by mass of the total amount of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. The blending ratio of at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate is, for example, 15 parts by mass or more and, for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0200] The aliphatic polyisocyanate derivative can be produced by a known method.

[0201] The average number of isocyanate groups in the aliphatic polyisocyanate derivative is 2 or more, preferably 2.5 or more, more preferably 2.9 or more, and is, for example, 3.8 or less. If the average number of isocyanate groups is equal to or greater than the lower limit, water repellency can be further improved. The average number of isocyanate groups is calculated from the isocyanate group concentration A of the aliphatic polyisocyanate derivative, the solid content concentration B, and the number average molecular weight C measured by gel permeation chromatography using the following equipment and conditions, according to the following formula (1). When two or more aliphatic polyisocyanate derivatives are used in combination, the average number of isocyanate groups is calculated from the weight ratio of the aliphatic polyisocyanate derivatives and the average number of isocyanate functional groups thereof.

[0202] Average number of isocyanate functional groups = A / B × C / 42.02 (1) (In the formula, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solid content concentration, and C represents the number average molecular weight.)

[0203] (Measurement conditions for number average molecular weight) Device: HLC-8220GPC (Tosoh) Columns: TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (Tosoh) connected in series Detector: differential refractometer Injection volume: 100μL Eluent: tetrahydrofuran Flow rate: 0.8mL / min Temperature: 40℃ Calibration curve: Standard polyethylene oxide in the range of 106 to 22450 (manufactured by Tosoh, product name: TSK Standard Polyethylene Oxide)

[0204] The long-chain active hydrogen compound has both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.

[0205] The hydrocarbon group having 12 to 30 carbon atoms may be, for example, a linear or branched saturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkyl group), or a linear or branched unsaturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkenyl group).

[0206] The active hydrogen group may be, for example, a hydroxyl group.

[0207] Such a long-chain active hydrogen compound having both a hydrocarbon group and an active hydrogen group may be, for example, at least one of a linear saturated hydrocarbon group-containing active hydrogen compound, a branched saturated hydrocarbon group-containing active hydrogen compound, a linear unsaturated hydrocarbon group-containing active hydrogen compound, and a branched unsaturated hydrocarbon group-containing active hydrogen compound.

[0208] The linear saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear saturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol, and linear saturated hydrocarbon group-containing sorbitan esters such as sorbitan tristearate.

[0209] The branched-chain saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain saturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include branched-chain saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol.

[0210] The linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear unsaturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol.

[0211] The branched-chain unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain unsaturated hydrocarbon group having 12 to 30 carbon atoms, and examples thereof include phytol.

[0212] The long-chain active hydrogen compound is preferably one or both of a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound. The long-chain active hydrogen compound can be used alone or in combination of two or more types.

[0213] When a long-chain active hydrogen compound is used alone, preferably a linear saturated hydrocarbon group-containing active hydrogen compound is used alone, more preferably a linear saturated hydrocarbon group-containing alcohol is used alone, and even more preferably stearyl alcohol is used alone. When two or more long-chain active hydrogen compounds are used in combination, preferably a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound are used in combination, more preferably a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, or a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester and a linear unsaturated hydrocarbon group-containing alcohol are used in combination.

[0214] When a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, more preferably 70 parts by mass or more, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 60 parts by mass or less, preferably 45 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. When the blending ratio of the linear saturated hydrocarbon group-containing alcohol is equal to or greater than the lower limit, the crystallinity of the hydrocarbon group is improved, resulting in improved water repellency.

[0215] When a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester, and a linear unsaturated hydrocarbon group-containing alcohol are used in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 30 parts by mass or more and, for example, 60 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear saturated hydrocarbon group-containing sorbitan ester is, for example, 20 parts by mass or more and, for example, 50 parts by mass or less, per 100 parts by mass of the total of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more and, for example, 20 parts by mass or less, relative to 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol.

[0216] When two or more long-chain active hydrogen compounds are used in combination, it is more preferable to use a linear saturated hydrocarbon group-containing alcohol in combination with a linear unsaturated hydrocarbon group-containing alcohol, and it is particularly preferable to use stearyl alcohol in combination with oleyl alcohol.

[0217] The cationic active hydrogen compound has both an active hydrogen group and a cationic group. The cationic active hydrogen compound can be used alone or in combination of two or more kinds.

[0218] As described above, the active hydrogen group is an active hydrogen group that reacts with an aliphatic polyisocyanate derivative, and examples thereof include hydroxyl groups. The cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule. Furthermore, examples of the cationic group include tertiary amino groups. That is, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. Such a cationic active hydrogen compound can impart good dispersibility in water and can also introduce cationic groups that have affinity for fibers, thereby improving washing durability.

[0219] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, and preferably N-methyldiethanolamine.

[0220] The acid compound is a compound that forms a salt with a cationic group. Examples of the acid compound include one or both of an organic acid and an inorganic acid. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, and malic acid, and preferably acetic acid or lactic acid, and more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and preferably hydrochloric acid. The acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid volatilizes by heat treatment, thereby reducing ionicity and improving water resistance, thereby improving water repellency. Furthermore, the acid volatilizes by heat treatment, making it easier for the cationic group to adsorb to the fiber, and thereby improving washing durability. The acid compounds can be used alone or in combination of two or more types.

[0221] A urethane-based compound is obtained as a reaction product by reacting the aliphatic polyisocyanate derivative with a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. To react the aliphatic polyisocyanate derivative with the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound, the long-chain active hydrogen compound is first blended with the aliphatic polyisocyanate derivative, and the aliphatic polyisocyanate derivative is then reacted with the long-chain active hydrogen compound. In this case, for example, when the isocyanurate derivative of the aliphatic polyisocyanate has an average of three isocyanate groups, the long-chain active hydrogen compound is preferably blended so that two isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate are modified by the long-chain active hydrogen compound to hydrocarbon groups having 12 to 30 carbon atoms, leaving one isocyanate group in the isocyanurate derivative of the aliphatic polyisocyanate and no unreacted isocyanurate derivative of the aliphatic polyisocyanate. Specifically, a long-chain active hydrogen compound is blended with an aliphatic polyisocyanate derivative so that the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less. As a result, the molecular terminals of the reaction product of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound (hereinafter referred to as the first intermediate reaction product) are hydrocarbon groups and isocyanate groups having 12 to 30 carbon atoms.

[0222] The reaction is carried out under a nitrogen atmosphere. The reaction conditions include a reaction temperature of, for example, 70°C to 120°C, and a reaction time of 1 hour to 6 hours. The reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value. The isocyanate concentration can be measured using a potentiometric titrator by the n-dibutylamine method in accordance with JIS K-1556.

[0223] In the above reaction, a known solvent such as methyl ethyl ketone can also be added in an appropriate ratio.

[0224] Next, a cationic active hydrogen compound is added to the reaction solution containing the first intermediate reaction product, and the first intermediate reaction product is reacted with the cationic active hydrogen compound. At this time, the cationic active hydrogen compound is added to the first intermediate reaction product so that the equivalent ratio of isocyanate groups to active hydrogen groups in the cationic active hydrogen compound (isocyanate groups / active hydrogen groups) is, for example, 0.95 or more and, for example, 1.05 or less.

[0225] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions include a reaction temperature of, for example, 70°C to 120°C, and a reaction time of 0.5 to 4 hours. The above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is complete. A known solvent, such as methyl ethyl ketone, can also be added in an appropriate ratio to the above reaction. This produces a reaction product (hereinafter referred to as the second intermediate reaction product) between the first intermediate reaction product and the cationic active hydrogen compound. The second intermediate reaction product has a hydrocarbon group having 12 to 30 carbon atoms and a cationic group.

[0226] Next, an acid compound is blended with the second intermediate reaction product. The blending ratio of the acid compound is, for example, 0.5 mol or more, preferably 3 mol or more, and for example, 10 mol or less, preferably 4 mol or less, per mol of the cationic group of the cationic active hydrogen compound. As a result, the acid compound forms a salt with the cationic group of the second intermediate reaction product, and a reaction liquid containing a reaction product (i.e., a urethane-based compound) of the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound is obtained. The reaction product has a hydrocarbon group having from 12 to 30 carbon atoms and a cationic group. Furthermore, because the reaction product has a hydrocarbon group having from 12 to 30 carbon atoms, it can self-disperse (self-emulsify) in water without the use of a dispersant (emulsifier). In other words, the reaction product can be internally emulsified.

[0227] Next, while maintaining the temperature of the reaction liquid at, for example, 50°C or higher and 100°C or lower, water is added to the reaction liquid to emulsify it. Thereafter, the solvent is removed from the reaction liquid. This results in an aqueous dispersion containing the reaction product (i.e., a urethane-based compound). The solids concentration of the aqueous dispersion is, for example, 10% by mass or higher and, for example, 30% by mass or lower.

[0228] Such urethane compounds are reaction products obtained using long-chain active hydrogen compounds, and therefore have excellent water repellency, oil repellency, oil resistance, and stain resistance. Furthermore, such urethane compounds are reaction products obtained using cationic active hydrogen compounds, and therefore have improved affinity with fibers, resulting in excellent washing durability for fibers.

[0229] In such a urethane-based compound, the concentration of hydrocarbon groups is 30% or more and 85% or less, preferably 50% or less. If the concentration of hydrocarbon groups is equal to or greater than the above-mentioned lower limit, the water repellency can be improved. If the concentration of hydrocarbon groups is equal to or less than the above-mentioned upper limit, the stability of the urethane-based compound can be improved. The concentration of hydrocarbon groups can be calculated from the amounts of each component charged.

[0230] In the above description, the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound are first reacted to obtain a reaction liquid containing a first intermediate reaction product, the first intermediate reaction product is then reacted with a cationic active hydrogen compound to obtain a reaction liquid containing a second intermediate reaction product, and the second intermediate reaction product is then reacted with an acid compound. However, the order of the reactions is not particularly limited. For example, the aliphatic polyisocyanate derivative and the cationic active hydrogen compound can be reacted first, and then the long-chain active hydrogen compound and the acid compound can be reacted. Alternatively, the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound can be mixed together and reacted.

[0231] (Dendrimer compounds) The dendrimer-based compound may be, for example, a dendritic polymer compound having a structure that is radially and regularly branched from the center. The dendritic polymer compound may have linear or branched hydrocarbon groups with one or more carbon atoms at the terminal branches to achieve water repellency.

[0232] The dendritic polymer compound may be, for example, a "polymer extender" disclosed in International Publication No. 2014 / 160906. For example, a compound obtained by reacting at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or a mixture thereof with at least one isocyanate-reactive compound selected from the following formulas (Ia), (Ib), or (Ic) may be used.

[0233] [ka]

[0234] In the above formula, R 50 are each independently -H, R 51 , -C(O)R 51 , -(CH2CH2O) n (CH(CH3)CH2O) m R 52 , or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R 51 where n is independently 0 to 20, m is independently 0 to 20, and m+n is greater than 0. 51 are each independently a linear or branched alkyl group having 5 to 29 carbon atoms, which may contain one or more unsaturated bonds; R 52 are each independently —H or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds.

[0235] In addition, in formula (Ia), R 50 or R 52 At least one of the groups is -H.

[0236] In the above formula, R 53 are each independently -H, -R 51 , -C(O)R 51 , -(CH2CH2O(CH(CH3)CH2O)mR 52 , or -(CH2CH2O(CH(CH3)CH2OC(O)R 51 and R 54 are each independently -H, a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds, -(CH2CH2O) n’ (CH(CH3)CH2O) m’ R 52 , or -(CH2CH2O(CH(CH3)CH2OC(O)R 51 wherein each n' is independently 0 to 20, each m' is independently 0 to 20, and m+n is greater than 0.

[0237] In addition, in formula (Ib), R 52 , R 53 or R 54 At least one of the groups is -H.

[0238] In the above formula, R 55 -H, -C(O)R 51 , or -CH2C[CH2OR 50 ]3.

[0239] In addition, in formula (Ic), R 55 or R 50 At least one of the groups is -H.

[0240] The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimers thereof. Commercially available products such as "DESMODURN-100" (manufactured by Bayer, trade name), "Duranate THA-100" (manufactured by Asahi Kasei Corporation, trade name), and "Duranate 24A-100" (manufactured by Asahi Kasei Corporation, trade name) can be used. The reaction can be carried out, for example, at 80°C for one hour or more.

[0241] 2.1.2 Other ingredients The non-fluorine-based water-repellent component of the present disclosure includes a predetermined water-repellent component and may further include components suitable for performing an adhesion treatment on various articles. For example, these include a solvent (dispersion medium) and various additives. Note that these solvents and various additives may not remain on the surface of various water-repellent products after the water-repellent treatment. The aqueous medium may be water or a mixture of water and an organic solvent. The amount of organic solvent may be, for example, 0% by mass or more and 30% by mass or less, or 0% by mass or more and 10% by mass or less, relative to the aqueous medium. The aqueous medium may consist solely of water. The treatment liquid may also contain an acid, an alkali, a surfactant, a chelating agent, etc. The treatment liquid may also contain other water-repellent aids, other water-repellent components, a crosslinking agent, an antibacterial and deodorizing agent, a flame retardant, an antistatic agent, a softener, an antifungal agent, etc. In particular, when the treatment liquid contains a crosslinking agent, durable water repellency and other properties are likely to be even better. Crosslinking agents will be described later.

[0242] 2.1.3 Content of non-fluorinated water-repellent ingredients The content of the non-fluorine-based water-repellent component in the water-repellent treatment agent is not particularly limited. For example, the ratio (mass proportion) of the non-fluorine-based water-repellent component to the entire water-repellent treatment agent may be 0.1 to 70 mass %, or 0.5 to 50 mass %.

[0243] 2.2 Contact method In one embodiment of the method for producing a water-repellent textile product, the non-fluorine-based water-repellent component (the water-repellent treatment agent containing a non-fluorine-based water-repellent component) is brought into contact with the textile material after the pretreatment, thereby allowing the non-fluorine-based water-repellent component to adhere to the textile material. The method for bringing the non-fluorine-based water-repellent component (the water-repellent treatment agent containing a non-fluorine-based water-repellent component) into contact with the textile material can be the same as the method for contacting with the pretreatment agent described in 1.3.

[0244] 2.3 Heat treatment It is preferable that the fiber material be thoroughly dried after contact with the water-repellent component. The temperature for the dry heat treatment is preferably 100 to 200°C, and particularly preferably 120 to 180°C. The time for the dry heat treatment is preferably 10 seconds to 3 minutes, and particularly preferably 1 to 2 minutes. The method for the dry heat treatment is not particularly limited, but a tenter is preferred when the material to be treated is in the form of a fabric.

[0245] 2.4 Adhesion amount A non-fluorine-based water-repellent component adheres to the textile material after the water-repellent treatment. The treatment with the water-repellent treatment agent is preferably carried out in an amount such that the amount of the non-fluorine-based water-repellent component adhered is 0.1 to 10 parts by mass or 0.5 to 5 parts by mass per 100 parts by mass of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0246] 3. Use of crosslinking agents In one embodiment, the method for producing a water-repellent textile product, particularly when improving durable water repellency, preferably includes, in addition to pretreating and water-repellent treating the textile material, applying a crosslinking agent containing methylolmelamine, an isocyanate group, or a compound having two or more blocked isocyanate groups to the textile material and heating the resulting material. Furthermore, when further improving durable water repellency, the pretreatment agent or water-repellent treating agent preferably contains a non-fluorine-based polymer copolymerized with a monomer having a functional group reactive with the crosslinking agent. Examples of compounds having two or more isocyanate groups are as described above. The crosslinking agent may be used alone or in combination.

[0247] The crosslinking agent can be attached to the object to be treated (textile product) by, for example, immersing the object to be treated in a treatment liquid prepared by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing the crosslinking agent in water, and then drying the treatment liquid attached to the object to be treated. The crosslinking agent attached to the object to be treated can then be heated to promote a reaction between the crosslinking agent and the object to be treated and the non-fluorine-based water-repellent component. To promote the crosslinking agent reaction sufficiently and more effectively improve durable water repellency, the heating is preferably performed at 110 to 180°C for 1 to 5 minutes. The steps of attaching the crosslinking agent and heating may be performed simultaneously with the treatment step with the water-repellent treatment agent described above. When performing these steps simultaneously, for example, a treatment liquid containing the non-fluorine-based water-repellent component and the crosslinking agent is attached to the object to be treated, the water is removed, and then the crosslinking agent attached to the object to be treated is heated. Considering simplification of the water-repellent treatment process, reduction of heat consumption, and economic efficiency, it is preferable to perform these steps simultaneously with the treatment step with the water-repellent treatment agent.

[0248] However, excessive use of the crosslinking agent may impair the feel, and the crosslinking agent is preferably used in an amount of 0.01 to 50 parts by mass, or 0.1 to 10 parts by mass, per 100 parts by mass of the material to be treated (textile product).

[0249] 4.Applications The water-repellent textile products manufactured through the above-mentioned pretreatment and water-repellent treatment have excellent water repellency (initial water repellency and durable water repellency). Furthermore, since these water-repellent textile products do not use fluorine-based compounds, they can be said to be environmentally friendly. Because of their excellent water repellency, these water-repellent textile products are suitable for a variety of applications, including clothing and non-clothing items, such as down jacket coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying rack covers, curtains, and tents. [Example]

[0250] As described above, one embodiment of the technology of the present disclosure has been described, but the technology of the present disclosure can be modified in various ways other than the above embodiment without departing from the gist thereof. Below, the technology of the present disclosure will be described in more detail while showing examples, but the technology of the present disclosure is not limited to the following examples.

[0251] 1.Preparing the pretreatment agent The following polyester copolymers (polymer P) having anionic groups were synthesized (Synthesis Examples A-1 to A-9, Comparative Synthesis Examples A-1 to A-7). 25.0 parts by mass of the polyester copolymers obtained in the Synthesis Examples and Comparative Synthesis Examples and 75.0 parts by mass of water were charged into a reaction vessel and mixed uniformly at 80 to 90°C to obtain dispersions (pretreatment agents) containing 25% by mass of the polyester copolymer (Preparation Examples A-1 to A-9, Comparative Preparation Examples A-1 to A-7).

[0252] 1.1 Synthesis example A-1 A reaction vessel was charged with 155.4 g (0.8 mol) of dimethyl terephthalate, 59.2 g (0.2 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate. The mixture was stirred under a nitrogen atmosphere and heated from 150 °C to 230 °C over approximately 3 hours to carry out an ester exchange reaction, during which volatiles were distilled off. Next, 0.1 g of tetrabutyl titanate was added, and the pressure was gradually reduced to approximately 10 kPa. The reaction was continued at 250 °C for 2 hours, yielding approximately 224 g of polyester copolymer. The resulting polyester copolymer had a dicarboxylic acid unit content of approximately 72% by mass and a weight-average molecular weight of 19,000.

[0253] 1.2 Synthesis example A-2 A reaction was carried out in the same manner as in Preparation Example 1, except that 165.1 g (0.85 mol) of dimethyl terephthalate, 44.4 g (0.15 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 12 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were placed in a reaction vessel. Approximately 219 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 71 mass%, and the weight-average molecular weight was 6,500.

[0254] 1.3 Synthesis example A-3 A reaction was carried out in the same manner as in Preparation Example 1, except that 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 31 g of ethylene glycol, 52 g of neopentyl glycol, 12 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were placed in a reaction vessel. Approximately 235 g of a polyester copolymer was obtained by the same reaction as in Preparation Example 1. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 65% ​​by mass, and the weight-average molecular weight was 65,000.

[0255] 1.4 Synthesis example A-4 A reaction was carried out in the same manner as in Preparation Example 1, except that 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 106 g of diethylene glycol, and 0.1 g of zinc acetate were charged into a reaction vessel, to obtain approximately 244 g of a polyester copolymer. The content of dicarboxylic acid component units in the obtained polyester copolymer was approximately 62 mass%, and the weight-average molecular weight was 9,000.

[0256] 1.5 Synthesis example A-5 A reaction was carried out in the same manner as in Preparation Example 1, except that 116.5 g (0.6 mol) of dimethyl terephthalate, 49.8 g (0.3 mol) of isophthalic acid, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 12 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were charged into a reaction vessel. Approximately 214 g of a polyester copolymer was obtained by carrying out the reaction in the same manner as in Preparation Example 1. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 70 mass%, and the weight-average molecular weight was 16,000.

[0257] 1.6 Synthesis example A-6 A reaction was carried out in the same manner as in Preparation Example 1, except that 155.4 g (0.8 mol) of dimethyl terephthalate, 14.6 g (0.1 mol) of adipic acid, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 49.6 g of ethylene glycol, 20.8 g of neopentyl glycol, and 0.1 g of zinc acetate were charged into a reaction vessel, yielding approximately 206 g of a polyester copolymer. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 71 mass%, and the weight-average molecular weight was 22,000.

[0258] 1.7 Synthesis example A-7 A reaction was carried out in the same manner as in Preparation Example 1, except that 145.7 g (0.75 mol) of dimethyl terephthalate, 31.5 g (0.15 mol) of trimellitic acid, 23.0 g (0.1 mol) of dodecanedioic acid, 23 g of ethylene glycol, 23 g of 1,4-butanediol, 39 g of neopentyl glycol, and 0.1 g of zinc acetate were charged into a reaction vessel. Approximately 228 g of a polyester copolymer was obtained by carrying out the reaction in the same manner as in Preparation Example 1. The content of dicarboxylic acid component units in the obtained polyester copolymer was approximately 68% by mass, and the weight-average molecular weight was 2,800.

[0259] 1.8 Synthesis example A-8 A reaction was carried out in the same manner as in Preparation Example 1, except that 172.8 g (0.89 mol) of dimethyl terephthalate, 23.1 g (0.11 mol) of trimellitic acid, 39 g of ethylene glycol, 39 g of neopentyl glycol, and 0.1 g of zinc acetate were charged into a reaction vessel, to obtain approximately 213 g of a polyester copolymer. The content of dicarboxylic acid component units in the obtained polyester copolymer was approximately 69 mass%, and the weight-average molecular weight was 4,100.

[0260] 1.9 Synthesis example A-9 A reaction was carried out in the same manner as in Preparation Example 1, except that 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 49.6 g of ethylene glycol, 120 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were charged into a reaction vessel, and approximately 310 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 51% by mass, and the weight-average molecular weight was 10,000.

[0261] 1.10 Comparative synthesis example A-1 A reaction was carried out in the same manner as in Preparation Example 1, except that 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 24 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were charged into a reaction vessel, to obtain approximately 256 g of a polyester copolymer. The content of dicarboxylic acid component units in the obtained polyester copolymer was approximately 71 mass%, and the weight-average molecular weight was 29,000.

[0262] 1.11 Comparative synthesis example A-2 A reaction was carried out in the same manner as in Preparation Example 1, except that 126.2 g (0.65 mol) of dimethyl terephthalate, 103.6 g (0.35 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 120 g of polyethylene glycol having a molecular weight of 600, and 0.1 g of zinc acetate were placed in a reaction vessel. Approximately 347 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 53 mass%, and the weight-average molecular weight was 41,000.

[0263] 1.12 Comparative synthesis example A-3 A reaction was carried out in the same manner as in Preparation Example 1, except that 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, 310 g of polyethylene glycol having a molecular weight of 3100, and 0.1 g of zinc acetate were charged into a reaction vessel, and approximately 512 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 32 mass%, and the weight-average molecular weight was 85,000.

[0264] 1.13 Comparative synthesis example A-4 A reaction was carried out in the same manner as in Preparation Example 1, except that 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of dimethyl 5-sulfoisophthalate sodium salt, 57 g of ethylene glycol, 86 g of polyethylene glycol having a molecular weight of 1,000, and 0.1 g of zinc acetate were placed in a reaction vessel. Approximately 314 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 59 mass%, and the weight-average molecular weight was 31,000.

[0265] 1.14 Comparative synthesis example A-5 A reaction was carried out in the same manner as in Preparation Example 1, except that 186.2 g (0.96 mol) of dimethyl terephthalate, 11.8 g (0.04 mol) of dimethyl 5-sulfoisophthalate sodium salt, 31 g of ethylene glycol, 12 g of polyethylene glycol having a molecular weight of 600, 52 g of neopentyl glycol, and 0.1 g of zinc acetate were charged into a reaction vessel, and approximately 229 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 64 mass%, and the weight-average molecular weight was 19,000.

[0266] 1.15 Comparative synthesis example A-6 A reaction was carried out in the same manner as in Preparation Example 1, except that 135.8 g (0.7 mol) of dimethyl terephthalate, 88.8 g (0.3 mol) of dimethyl 5-sulfoisophthalate sodium salt, 62 g of ethylene glycol, and 0.1 g of zinc acetate were charged into a reaction vessel, and approximately 223 g of a polyester copolymer was obtained. The content of dicarboxylic acid component units in the resulting polyester copolymer was approximately 76 mass%, and the weight-average molecular weight was 30,000.

[0267] Table 1 below shows the amount (mol %) of units derived from specific dicarboxylic acids (dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group) in all dicarboxylic acid units, the intramolecular content of the dicarboxylic acid units in the polyester copolymer, and the weight average molecular weight of the polyester copolymer for each of the above synthesis examples and comparative synthesis examples.

[0268] [Table 1]

[0269] 2.Preparing the water repellent treatment As a water-repellent treatment agent, a treatment liquid containing the following non-fluorine-based water-repellent component was prepared.

[0270] 2.1 Preparation of acrylic compound dispersion (Preparation example B-1) An autoclave was charged with 15.6 parts by weight of stearyl acrylate, 0.4 parts by weight of diacetone acrylamide, 0.8 parts by weight of Noigen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 0.2 parts by weight of stearyl trimethylammonium sulfate, 10 parts by weight of tripropylene glycol, and 68.8 parts by weight of water, and the mixture was stirred at 45 °C to obtain a mixed solution. Ultrasonic waves were irradiated to the mixed solution to emulsify and disperse all the monomers. Next, 0.2 parts by weight of azobis(isobutylamidine) dihydrochloride was added to the dispersion, and radical polymerization was carried out at 60 °C for 6 hours under a nitrogen atmosphere while continuously injecting 4.0 parts by weight of vinyl chloride into the autoclave to maintain the internal pressure at 0.3 MPa, to obtain a dispersion containing 20% ​​by weight of acrylic resin.

[0271] (Preparation Examples B-2 and B-3) According to the amounts of ingredients shown in Table 2 below, a dispersion containing 20% ​​by mass of acrylic resin was obtained in the same manner as in Preparation Example B-1.

[0272] [Table 2]

[0273] 2.2 Preparation of silicone compound dispersion 2.2.1 Alkyl-modified silicone dispersion (Preparation Example B-4: Octadecyl Dimethicone Dispersion) SiH:SiCH3 molar ratio = 5:5 ( 1 Methyl hydrogen silicone (measured by H NMR (nuclear magnetic resonance)) and a hydrosilylation catalyst, a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene, were placed in a flask so that the platinum concentration in the reaction mixture was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-octadecene was added dropwise to the mixture in the flask for every 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to produce the product R in the following formula (1). 20 , R 21 and R22 is CH3 and R 23 C 18 H 37 a is 40, b is 40, a:b is 1:1, and R 30 ~R 35 An alkyl-modified silicone in which the alkyl group was CH3 was obtained. Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to FT-IR (Fourier transform infrared) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

[0274] [ka]

[0275] 20 parts by weight of the obtained alkyl-modified silicone, 1.2 parts by weight of SPAN40 (sorbitan-based nonionic surfactant, HLB=6.7), 1.3 parts by weight of TWEEN (registered trademark) 40 (sorbitan-based nonionic surfactant, HLB=15.6), 0.5 parts by weight of Noigen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.5 parts by weight of Noigen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 parts by weight of stearyl trimethylammonium sulfate, and 10 parts by weight of dipropylene glycol were mixed under heating. Next, 66.0 parts by weight of water was added little by little to the obtained mixture while mixing, to obtain a dispersion containing 20% ​​by weight of octadecyl dimethicone (average HLB of nonionic surfactants=11.4).

[0276] (Preparation Example B-5: Hexacosyl Dimethicone Dispersion) SiH:SiCH3 molar ratio = 4:6 ( 1Methyl hydrogen silicone (measured by H NMR (nuclear magnetic resonance)) and a hydrosilylation catalyst, a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene, were placed in a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-hexacosene was added dropwise to the mixture in the flask for 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain the product R in the above formula (1). 20 , R 21 and R 22 is CH3 and R 23 C 26 H 53 a is 60, b is 90, a:b is 2:3, and R 30 ~R 35 An alkyl-modified silicone in which the alkyl group was CH3 was obtained. Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to FT-IR (Fourier transform infrared) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

[0277] Using the obtained alkyl-modified silicone, a dispersion containing 20 mass % of hexacosyl dimethicone was obtained in the same manner as in Preparation Example B-4 (average HLB of the nonionic surfactants = 9.8).

[0278] (Preparation Example B-6: Dotriacontyl Dimethicone Dispersion) SiH:SiCH3 molar ratio = 3:7 ( 1 Methyl hydrogen silicone (measured by H NMR (nuclear magnetic resonance)) and a hydrosilylation catalyst, a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene, were placed in a flask so that the platinum concentration in the reaction mixture was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-dotriacontene was added dropwise to the mixture in the flask for every molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain the product R in the above formula (1). 20 , R21 , R 22 is CH3 and R 23 C 32 H 65 a is 140, b is 60, a:b is 7:3, and R 30 ~R 35 An alkyl-modified silicone in which the alkyl group was CH3 was obtained. Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to FT-IR (Fourier transform infrared) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

[0279] Using the obtained alkyl-modified silicone, a dispersion containing 20 mass % dotriacontyl dimethicone was obtained in the same manner as in Preparation Example B-4 (average HLB of the nonionic surfactants = 8.1).

[0280] Table 3 below shows the compositions of Preparation Examples B-4 to B-6 and the average HLB of the nonionic surfactants.

[0281] [Table 3]

[0282] 2.2.2 Dispersion of silicone resin, dimethyl silicone, and amino-modified silicone (Preparation example B-7) 5.8 parts by mass of MQ-1600 (trimethylsilyl group-containing polysiloxane, Toray Dow Corning Co., Ltd.) as a silicone resin and 13.4 parts by mass of KF-96A-100cs (Shin-Etsu Silicones Co., Ltd.) as a dimethyl silicone were added to a 300 mL stainless steel pot and heated and stirred until the silicone resin was uniformly dissolved. 0.8 parts by mass of KF-8012 (Shin-Etsu Chemical Co., Ltd., both terminally amino-modified silicone, functional group equivalent weight 2200) as an amino-modified silicone was added to the resulting homogeneous solution to obtain a mixture. Next, 1.6 parts by mass of Noigen XL-40 was added, and 78.4 parts by mass of water were added in small portions while mixing. The mixture was sonicated using an ultrasonic emulsifier at 60-70°C for 10 minutes and then cooled to room temperature to obtain a dispersion containing 20% ​​by mass of silicone compounds (average HLB value of nonionic surfactants = 10.5).

[0283] (Preparation example B-8) A dispersion containing 20 mass % of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 4 below was used (average HLB of the nonionic surfactants = 4.7).

[0284] (Preparation example B-9) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 4 below was used (average HLB of the nonionic surfactants = 18.3).

[0285] (Preparation example B-10) A dispersion containing 20 mass % of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the blending ratio shown in Table 4 below was used (average HLB of the nonionic surfactants = 10.5).

[0286] 2.2.3 Amino-modified silicone dispersion (Preparation example B-11) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that WACKER FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicones, amine equivalent 3700, solids content 100%) was used as the amino-modified silicone and the blending ratio shown in Table 3 below was used (average HLB of the nonionic surfactants = 12.0).

[0287] 2.2.4 Silicone resin dispersion (Preparation example B-12) A dispersion containing 20% ​​by mass of silicone resin was obtained in the same manner as in Preparation Example A-7, except that IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) was used as the solvent and the blending ratio shown in Table 3 below was used (average HLB of the nonionic surfactants = 4.7).

[0288] [Table 4] The nonionic surfactants are SPAN65: HLB 2.1 (manufactured by Croda), Noigen XL-160: HLB 16.3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and NIKKOL BC-30: HLB 19.5 (manufactured by Nikko Chemicals Co., Ltd.). Noigen XL-40 is as described above.

[0289] 2.3 Preparation of dispersion of wax-based compounds (Preparation example B-13) A high-pressure reactor was charged with 20 parts by mass of Paraffin Wax-155 (manufactured by Nippon Seiro Co., Ltd., melting point 69°C), 78 parts by mass of water, 1.0 part by mass of sorbitan monostearate (HLB=4.5), and 1.0 part by mass of polyoxyethylene sorbitan monostearate (HLB=14.9), and sealed. The temperature inside the vessel was then raised to 110-120°C with stirring. After that, high-pressure emulsification was performed for 30 minutes while maintaining high pressure inside the vessel, yielding an emulsion containing 20% ​​by mass of paraffin wax (average HLB of nonionic surfactants=9.7).

[0290] 2.4 Preparation of urethane compound dispersion 2.4.1 Polyurethane resin synthesis (Synthesis example U-1) In a reactor equipped with a thermometer, stirrer, nitrogen inlet, and condenser, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., product name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, a hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (an organic phosphite ester, a cocatalyst) were mixed under a nitrogen atmosphere. 10.7 parts by mass of 1,3-butanediol was then added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, after which it was cooled to 60°C. 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanurate catalyst, and the mixture was allowed to react for 1.5 hours. Next, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer was 0.5% or less, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functionality of 3.0.

[0291] 2.4.2 Preparation of polyurethane resin dispersion (Preparation example B-14) A reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube was mixed with 100.08 parts by mass of the aliphatic polyisocyanate derivative of Synthesis Example U-1 as an aliphatic polyisocyanate derivative and 90.03 parts by mass of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound, and the mixture was reacted in a nitrogen atmosphere at 110°C for 4 hours until the isocyanate group concentration reached 3.67%. The reaction solution was then cooled to 80°C, and 9.89 parts by mass of N-methyldiethanolamine as a cationic active hydrogen compound was added. The mixture was reacted at 80°C for 1 hour. 50 parts by mass of methyl ethyl ketone was added as a solvent, and the mixture was reacted at 80°C until disappearance of the isocyanate groups was confirmed by infrared absorption spectroscopy. Next, 57.7 parts by mass of methyl ethyl ketone (MEK) was added to the reaction solution, the temperature was raised to 80°C, and the reaction solution was mixed until completely dissolved, after which it was cooled to 75°C. Thereafter, 18.93 parts by mass of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 20 parts by mass of NIKKOL Hexaglyn 1-SV (HLB=9.0, manufactured by Nikko Chemicals Co., Ltd.) was added and mixed, and 800 parts by mass of ion-exchanged water heated to 70°C was gradually added to the mixture to emulsify it. Next, MEK was distilled off under reduced pressure in an evaporator with a water bath temperature of 60°C. Next, the solids concentration was adjusted to 20% by mass with ion-exchanged water to obtain a dispersion containing a polyurethane resin (average HLB of nonionic surfactants=9.0, solids content 20% by mass).

[0292] 2.5 Preparation of dendrimer-based compound dispersion (Preparation example B-15) A four-neck round-bottom flask equipped with an overhead stirrer, thermocouple, and Dean-Stark condenser was charged with 15.3 parts by weight of sorbitan tristearate (hydroxyl number = 77.2 mg KOH / g) and 24.7 parts by weight of 4-methyl-2-pentanone (MIBK). The solution was refluxed for 1 hour to remove residual moisture. After 1 hour, the solution was cooled to 50°C, and 4.0 parts by weight of DESMODUR N-100 was added, followed by the catalyst. The solution was heated to 80°C for 1 hour more to obtain a dendrimer solution.

[0293] 52.7 parts by weight of water, 0.7 parts by weight of ARMEEN DM-18D, 2.0 parts by weight of TERGITOL TMN-10, and 0.6 parts by weight of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was then heated to 60°C. The dendrimer solution prepared above was cooled to 60°C, and the heated surfactant solution was slowly added to prepare a cloudy emulsion. After homogenization at 41.37 MPa (6000 psi), the solvent was removed by distillation under reduced pressure, yielding a dispersion containing 20% ​​dendrimer-based compound (average HLB of nonionic surfactants = 14.4, solids content 20% by weight).

[0294] 3. Treatment of fibers Polyester (PET) woven fabric was subjected to a dipping treatment, padding treatment, or dyeing / soaping / washing treatment using the pretreatment agent to obtain a pretreatment-treated fabric. The pretreatment-treated fabric was then subjected to a water-repellent treatment using a water-repellent treatment agent, and its water repellency was evaluated. The water-repellent treatment agent and crosslinker were diluted with water to prepare a treatment solution so that the water-repellent treatment agent content was 6% by mass and the NK Assist FU (crosslinker, Nicca Chemical Co., Ltd.) content was 1% by mass.

[0295] 3.1 Immersion Treatment (Examples 1 to 27, Comparative Examples 1 to 6) A pretreatment liquid was prepared by diluting the pretreatment agent with water to obtain the composition shown in Table 5 or 6 below. The treated fabric was then immersed in the pretreatment liquid at a bath ratio of 1:10 (by mass, the same applies below) at 80°C for 20 minutes (pretreatment). After the pretreatment, the fabric was dried at 130°C for 1 minute to obtain a fabric treated with the pretreatment agent. The water-repellent treatment liquid was then prepared by diluting the water-repellent treatment agent and crosslinking agent with water to obtain the composition shown in Table 5 or 6, and the fabric treated with the pretreatment agent was padded with the water-repellent treatment liquid (water-repellent treatment). After the water-repellent treatment, the fabric was dried at 170°C for 1 minute to obtain a water-repellent textile product.

[0296] 3.2 Padding Treatment (Example 28, Comparative Example 7) A pretreatment liquid was prepared by diluting the pretreatment agent with water to the composition shown in Table 6 below, and then a padding treatment was performed on treated fabric with the pretreatment liquid (pretreatment). After the pretreatment, the fabric was dried at 130°C for 1 minute to obtain a pretreatment agent-treated fabric. Subsequently, a water-repellent treatment liquid was prepared by diluting the water-repellent treatment agent and crosslinking agent with water to the composition shown in Table 6, and then a padding treatment was performed on the pretreatment agent-treated fabric with the water-repellent treatment liquid (water-repellent treatment). After the water-repellent treatment, the fabric was dried at 170°C for 1 minute to obtain a water-repellent textile product.

[0297] 3.3 Dyeing, soaping, and washing treatments (Examples 29 to 37, Comparative Examples 8 to 13) After the pretreatments (3.3.1 to 3.3.4) described below were carried out, a water-repellent treatment (3.3.5) was carried out to obtain a water-repellent textile product. 3.3.1 First embodiment (two-bath, two-stage process): Example 29, Comparative Examples 8 to 9 Polyester fibers were dyed and soaped using a two-bath, two-stage method.

[0298] 3.3.1.1 Dyeing process A 100% polyester fabric was used as the test cloth, and a mini color dyeing machine (manufactured by Rapid) was used as the test equipment. The test cloth was placed in a dyeing solution having the following composition so that the liquor ratio was 1:15, and the dyeing process was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0299] <Composition of staining solution> 80% acetic acid 0.4g / L Dyeing auxiliary NICCA SUNSOLT RM-3406 0.5g / L disperse dye Foron Rubine (manufactured by ARCHROMA) 4.5%owf

[0300] 3.3.1.2 Soaping process After the dyeing treatment, the dyeing solution was cooled to about 80°C and then drained. A new soaping solution having the following composition was prepared, and a soaping treatment was carried out at a bath ratio of 1:15 at 80°C for 20 minutes.

[0301] <Soaping liquid composition> Pretreatment agent 0 or 1g / L Caustic soda 48% 1.0g / L Sodium hydrosulfite 1.0g / L

[0302] 3.3.1.3 Cleaning process, etc. The polyester fiber after the soaping treatment was washed with water, dehydrated, and dried to obtain a dyed polyester fiber product. The washing liquid used for washing did not contain a pretreatment agent.

[0303] 3.3.2 Second embodiment (one-bath, two-stage process): Example 30, Comparative Examples 10 to 11 A dyeing treatment of polyester fibers was carried out using a dyeing assistant and a pretreatment agent in a dyeing solution, and then a soaping solution was prepared by adding chemicals to the dye bath, followed by a soaping treatment.

[0304] 3.3.2.1 Dyeing process A 100% polyester fabric was used as the test cloth, and a mini color dyeing machine (manufactured by Rapid) was used as the test equipment. The test cloth was placed in a dye bath having the following composition so that the bath ratio was 1:15, and dyeing was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0305] <Dye bath composition> 80% acetic acid 0.4g / L Dyeing auxiliary NICCA SUNSOLT RM-3406 0.5g / L Pretreatment agent 0 or 1g / L disperse dye Foron Rubine (manufactured by ARCHROMA) 4.5%owf

[0306] 3.3.2.2 Soaping process After the dyeing process, the dyeing solution was cooled to about 80°C, and the following chemicals were added to prepare a soaping solution, which was then soaped for 20 minutes at 80°C. Here, the following chemicals were added at 1g / L each so that the bath ratio of polyester fiber to soaping solution remained at 1:15.

[0307] <Drugs> Caustic soda 48% 1g / L Sodium hydrosulfite 1g / L

[0308] 3.3.2.3 Cleaning process, etc. The polyester fiber after the soaping treatment was washed with water, dehydrated, and dried to obtain a dyed polyester fiber product. The washing liquid used for washing did not contain a pretreatment agent.

[0309] 3.3.3 Third embodiment (one-bath, two-stage process): Examples 31 to 34, Comparative Examples 12 to 13 A dyeing treatment of polyester fibers was carried out in a dyeing solution using a dyeing assistant, and then a pretreatment agent and chemicals were added to the dye bath to prepare a soaping solution, followed by a soaping treatment.

[0310] 3.3.3.1 Dyeing process A 100% polyester fabric was used as the test cloth, and a mini color dyeing machine (manufactured by Rapid) was used as the test equipment. The test cloth was placed in a dyeing solution having the following composition so that the liquor ratio was 1:15, and the dyeing process was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0311] <Composition of staining solution> 80% acetic acid 0.4g / L Dyeing auxiliary NICCA SUNSOLT RM-3406 0.5g / L disperse dye Foron Rubine (manufactured by ARCHROMA) 4.5%owf

[0312] 3.3.3.2 Soaping process After the dyeing treatment, the dyeing solution was cooled to about 80°C, and the following chemicals were added to prepare a soaping solution, which was then soaped for 20 minutes at 80°C. Here, the following chemicals were added in the amounts shown below so that the bath ratio of polyester fiber to soaping solution remained at 1:15.

[0313] <Drugs> Pretreatment agent 1g / L Caustic soda 48% or soda ash 1 or 5g / L Sodium hydrosulfite or thiourea dioxide 1g / L

[0314] 3.3.3.3 Cleaning process The polyester fiber after the soaping treatment was washed with water, dehydrated, and dried to obtain a dyed polyester fiber product. The washing liquid used for washing did not contain a pretreatment agent.

[0315] 3.3.4 Others (One-bath, two-stage method): Examples 35 to 37 The above describes the case where only one type of predetermined pretreatment agent is added to the dyeing solution or soaping solution. Below, we will show the case where a pretreatment agent is added to the soaping solution and the cleaning solution used in the cleaning treatment (hot water washing and / or water rinsing) after the soaping treatment, and the case where a pretreatment agent is added to the cleaning solution used in the cleaning treatment (hot water washing and / or water rinsing) after the soaping treatment.

[0316] 3.3.4.1. Dyeing and soaping processes After dyeing in the same manner as in the third embodiment, the dyeing solution was cooled to about 80°C, and the following chemicals were added as desired to prepare a soaping solution, followed by soaping for 20 minutes at 80°C. The following chemicals were added in the amounts shown below so that the bath ratio of polyester fiber to soaping solution remained at 1:15.

[0317] Pretreatment agent 0 or 0.5g / L Caustic soda 48% 1g / L Sodium hydrosulfite 1g / L

[0318] 3.3.4.2 Cleaning process After the above soaping treatment, the following chemicals were added to prepare a washing solution, and then washing treatment with hot water at 80°C or water at 30°C was carried out for 20 minutes. The amounts of the following chemicals added were adjusted as follows so that the bath ratio of polyester fiber to washing solution was 1:15. Thereafter, dehydration and drying were carried out to obtain a polyester dyed fiber product.

[0319] <Drugs> Pretreatment agent 0.5g / L or 1g / L

[0320] 3.3.5 Water-repellent treatment After the pretreatments (3.3.1 to 3.3.4) were performed, the water-repellent treatment agent and crosslinking agent were diluted with water to prepare a treatment solution with the composition shown in Table 7, and the fabric treated with the pretreatment agent was padded with the treatment solution (water-repellent treatment). After the water-repellent treatment, the fabric was dried at 170°C for 1 minute to obtain a water-repellent textile product.

[0321] 4. Evaluation Method 4.1 Evaluation of initial water repellency The water repellency of the above water-repellent textile products was evaluated using a shower water temperature of 20°C according to the spray method of JIS L1092 (2009). The results were visually evaluated using the following grades. If the characteristics were slightly better, a "+" was given to the grade, and if the characteristics were slightly worse, a "-" was given to the grade. Water repellency: Condition 5: No adhesion or wetness on the surface 4: Slight adhesion and wetting on the surface 3: Shows partial surface wetting 2: Surface wetness 1: Shows wetting of the entire surface 0: Both sides are completely wet

[0322] 4.2 Evaluation of durable water repellency The above water-repellent textile products were washed 20 times (L-20) according to the 103 method of JIS L0217 (1995), and the water repellency after air drying was evaluated according to the same procedure and grade as above.

[0323] 4.3 Evaluation of rubbing fastness The above water-repellent textile products were evaluated for dry and wet rubbing fastness. Dry and wet rubbing fastness was measured using the JIS L0849:2013 rubbing tester type II (Gakushin type) method, and fastness was determined using the stain gray scale (JIS L0805:2005). The higher the rating grade, the better the fastness. Each grade was divided into four to express subtle differences in fastness. For example, grades 4 and 5 were expressed as 4.3, 4.5, and 4.8. The same applies to the other grades.

[0324] 4.4 Evaluation of mechanical stability The water-repellent treatment agent (Preparation Example B-3) and pre-treatment agents (Preparation Examples A-1 to A-9, Comparative Preparation Examples A-1 to A-6) were diluted with tap water to prepare 500 mL solutions (Examples 38 to 46, Comparative Examples 14 to 19) so that the compositions were as shown in Table 8. This was stirred for 10 minutes at 5,000 rpm in a homomixer, and the resulting scum was filtered onto a black cotton cloth, and the aggregates remaining on the surface of the cotton cloth were visually inspected. 5: No agglomerates 4: Slight agglomeration 3: Overall light whitening 2: Overall white aggregates remain 1: Unfilterable

[0325] 5. Evaluation Results The evaluation results are shown in Tables 5 to 8 below.

[0326] [Table 5]

[0327] [Table 6]

[0328] [Table 7]

[0329] [Table 8]

[0330] The results shown in Tables 5 to 8 reveal the following: (1) When a polyester copolymer having a predetermined anionic group is treated on a textile material and then subjected to a water-repellent treatment with a water-repellent treating agent (Examples 1 to 37), the initial water repellency, washing-durable water repellency, and friction fastness of the water-repellent textile products are improved compared to Comparative Examples 1 to 13. (2) The effects of the above pretreatment are not dependent on the type of treatment, and the same effect can be obtained when the fabric is subjected to a dipping treatment (Examples 1 to 27), a padding treatment (Example 28), or one or more of a dyeing treatment, a soaping treatment, and a washing treatment (Examples 29 to 37). (3) The pretreatment agent can perform water-repellent treatment without reducing the stability of the water-repellent bath (Examples 38 to 46, Comparative Examples 14 to 19).

[0331] From the above results, it can be said that a textile product having excellent water repellency can be produced by a method for producing a textile product which includes contacting a textile material with a polyester copolymer having an anionic group, and contacting the textile material after contacting with the polyester copolymer having an anionic group with a non-fluorinated water-repellent component.

[0332] In the above examples, a polyester copolymer having an anionic group and a non-fluorinated water-repellent component are used to impart water repellency to a textile product, but the technology of the present disclosure is not limited to this example. The treatment method of the present disclosure is believed to be capable of imparting excellent initial water repellency and durable water repellency to various articles other than textile materials. In particular, as shown in the above examples, the method is suitable for imparting durable water repellency to textile materials.

Claims

1. contacting a textile material with a polyester copolymer having anionic groups; and contacting the textile material with a non-fluorine-based water-repellent component after contacting with the polyester copolymer having an anionic group; A method for producing a water-repellent textile product, comprising: The polyester copolymer contains dicarboxylic acid units and diol units, the dicarboxylic acid units contain 5 mol % or more and 30 mol % or less of at least one of units derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, and units derived from a tricarboxylic acid, the diol units are derived from a diol having a molecular weight of 48 to 900, and the polyester copolymer has an intramolecular content of the dicarboxylic acid unit of 50% by mass or more and 75% by mass or less; A method for manufacturing water-repellent textile products.

2. Contacting a polyester copolymer having an anionic group with a polyester-based fiber; and contacting the polyester fiber with a non-fluorine-based water-repellent component after contacting the polyester fiber with the polyester copolymer having an anionic group; A method for producing a water-repellent textile product, comprising: The method for contacting the polyester copolymer having an anionic group includes: Dyeing polyester fibers, The polyester fiber after the dyeing treatment is subjected to a soaping treatment in the same bath as the dyeing solution or in a separate bath; and subjecting the polyester fiber after the soaping treatment to one or both of a hot water washing treatment and a water washing treatment; Including, one or both of a soaping liquid used in the soaping treatment and a cleaning liquid used in the cleaning treatment contain the polyester copolymer having an anionic group; the polyester copolymer having an anionic group contains a dicarboxylic acid unit and a diol unit, the dicarboxylic acid units contain 5 mol % or more and 30 mol % or less of at least one of units derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate salt group, and units derived from a tricarboxylic acid, the diol unit is derived from a diol having a molecular weight of 48 or more and 900 or less, and the content ratio of the dicarboxylic acid unit in the molecule of the polyester copolymer having an anionic group is 50% by mass or more and 75% by mass or less; A method for manufacturing water-repellent textile products.

3. A method for producing the water-repellent textile product according to claim 2, The polyester fiber after the dyeing treatment is subjected to the soaping treatment in the same bath as the dyeing solution, the dyeing solution used in the dyeing treatment contains the polyester copolymer having an anionic group, and At least a part of the polyester copolymer having an anionic group contained in the dyeing solution is used as at least a part of the polyester copolymer having an anionic group contained in the soaping solution. A method for manufacturing water-repellent textile products.

4. A method for producing the water-repellent textile product according to claim 2, and performing a soaping treatment of the polyester fiber having an anionic group after the dyeing treatment in the same bath as the dyeing solution, using the anionic group; The soaping solution used in the soaping treatment is prepared by adding at least the polyester copolymer having an anionic group to the dyeing solution after the dyeing treatment. A method for manufacturing water-repellent textile products.

5. the non-fluorine-based water-repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound; A method for producing the water-repellent textile product according to any one of claims 1 to 4.

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