Method for manufacturing water repellent fibrous product

Abstract

The present invention provides a method for producing a water repellent fiber product having excellent water repellency. The method for producing a water repellent fiber product comprises contacting a polyester copolymer having an anionic group with a fiber material, and contacting a non-fluorine water repellent component with the fiber material after the polyester copolymer having an anionic group is contacted.

Description

Technical Field

[0001] This invention discloses a method for manufacturing water-repellent fiber products. Background Technology

[0002] Fluorinated water repellents containing fluorinated groups are known. Treating articles such as textiles with fluorinated water repellents can impart excellent water repellency. Fluorinated water repellents are typically manufactured by polymerizing or copolymerizing monomers containing fluoroalkyl groups. To exhibit sufficient water repellency, the orientation of the fluoroalkyl groups needs to be adjusted; usually, after the fluorinated water repellent is applied to the article, heat treatment is performed at temperatures exceeding 130°C. However, such heat treatment is undesirable from an energy-saving perspective. Furthermore, monomers containing fluoroalkyl groups are not only expensive but also difficult to decompose, thus posing a significant environmental burden. Based on this situation, in recent years, techniques have been studied to impart excellent water repellency to articles such as textiles by treating them with non-fluorinated water repellents that do not contain fluorine. For example, Patent Document 1 proposes a water repellent formed by emulsifying and dispersing a specific non-fluorinated polymer, with the aim of imparting water repellency comparable to conventional fluorinated water repellents.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2006-328624 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, even the conventional non-fluorinated water repellents described in Patent Document 1 do not adequately impart water repellency to fiber products. Furthermore, for water-repellent fiber products, durability (durable water repellency) is required, ensuring that the water repellency is not diminished by outdoor use or washing. In this respect, the aforementioned conventional non-fluorinated water repellents are still insufficient.

[0008] Problem-solving methods

[0009] As a means to solve the above problems, the present invention discloses the following multiple embodiments.

[0010] <Method 1>

[0011] A method for manufacturing a water-repellent fiber article includes contacting a polyester copolymer having anionic groups with a fiber material, and contacting the fiber material after contacting the polyester copolymer having anionic groups with a non-fluorinated water-repellent component. The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises at least 5 mol% and 30 mol% of at least one of the following units: 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; the diol unit is derived from a diol with a molecular weight of 48 or more and 900 or less. The dicarboxylic acid unit in the polyester copolymer contains more than 50% by mass and less than 75% by mass.

[0012] <Method 2>

[0013] A method for manufacturing a water-repellent fiber article includes contacting a polyester copolymer having anionic groups with polyester fibers, and contacting the polyester fibers after contacting the polyester copolymer having anionic groups with a non-fluorinated water-repellent component. The method of contacting a polyester copolymer having anionic groups comprises: Dyeing process for polyester fibers; The polyester fibers after the dyeing treatment are subjected to a soaping treatment in the same bath or a different bath as the dyeing solution; and The polyester fibers after the soaping treatment are subjected to one or both of the following cleaning treatments: hot water washing and water washing. One or both of the soaping solution used in the soaping treatment and the cleaning solution used in the cleaning treatment contain the polyester copolymer having anionic groups. The polyester copolymer having anionic groups comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises at least 5 mol% and less than 30 mol% of at least one of the following units: units derived from dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group, and units derived from tricarboxylic acids. The diol unit is derived from diols with a molecular weight of 48 or more and 900 or less, and, The dicarboxylic acid unit in the polyester copolymer having anionic groups contains 50% by mass or more and 75% by mass or less in the molecule.

[0014] <Method 3>

[0015] The method for manufacturing water-repellent fiber products according to method 2 includes...

[0016] The polyester fibers after the dyeing treatment are subjected to the soaping treatment in the same bath as the dyeing solution. The dyeing solution used in the dyeing process contains the polyester copolymer having anionic groups, and At least a portion of the polyester copolymer with anionic groups contained in the dyeing solution is used as at least a portion of the polyester copolymer with anionic groups contained in the soaping solution.

[0017] <Method 4>

[0018] The method for manufacturing water-repellent fiber products according to method 2 or 3 includes,

[0019] For the polyester fibers with anionic groups after dyeing, a soaping treatment with anionic groups is performed in the same bath as the dyeing solution, and...

[0020] The soaping solution used in the soaping process is prepared by adding at least the polyester copolymer having anionic groups to the dyeing solution after the dyeing process.

[0021] <Method 5>

[0022] According to any one of the methods 1 to 4, the non-fluorinated water-repellent component is at least one of acrylic compounds, organosilicon compounds, wax compounds, carbamate compounds, and dendritic macromolecular compounds.

[0023] Invention Effects

[0024] According to the manufacturing method of this disclosure, water-repellent fiber products with excellent water repellency (initial water repellency and durable water repellency) can be manufactured. It is considered that by contacting a polyester copolymer with anionic groups with the fiber material, and then contacting the non-fluorinated water-repellent component with the fiber material, excellent water repellency can be imparted to the fiber material. Furthermore, according to the technology of this disclosure, products with excellent rubbing fastness or mechanical stability can also be manufactured. Detailed Implementation

[0025] The following describes a method for manufacturing a water-repellent fiber product according to one embodiment, but the method for manufacturing a water-repellent fiber product disclosed herein is not limited to this method.

[0026] One embodiment of a method for manufacturing a water-repellent fiber article includes contacting a polyester copolymer (polymer P) having anionic groups with a fiber material, and then contacting the fiber material after contact with the polyester copolymer having anionic groups with a non-fluorinated water-repellent component. In other words, one embodiment of a method for manufacturing a water-repellent fiber article involves pretreating the fiber material with a polyester copolymer having anionic groups, followed by water-repellent treatment with a non-fluorinated water-repellent component.

[0027] 1. Preprocessing

[0028] In one embodiment of a method for manufacturing a water-repellent fiber article, as a pretreatment, a polyester copolymer (polymer P) having anionic groups is brought into contact with the fiber material.

[0029] 1.1 Fiber Materials

[0030] There are no particular limitations on the type of fiber material. The fiber material can be at least one of the following: natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.); polyester; polyurethane; polypropylene; and their composite fibers and blended fibers. The fiber material can be in any form, such as fiber (tow, filament, etc.), filament, knitted fabric (including cross-knitted), woven fabric (including interwoven), nonwoven fabric, or paper. In one embodiment of the water-repellent fiber product, from the viewpoint of achieving superior water repellency, the fiber material preferably includes polyamide and polyester as raw materials, and particularly preferably at least one of the following: nylon 6, nylon 6,6, etc.; polyethylene terephthalate (PET), trimethyl terephthalate, polylactic acid, etc.; and blended fibers containing them.

[0031] 1.2 Pretreatment agent

[0032] In one embodiment of a method for manufacturing a water-repellent fiber article, a polyester copolymer (polymer P) having anionic groups is contacted with the fiber material. For example, a pretreatment agent comprising a polyester copolymer having anionic groups is prepared, and the pretreatment agent is contacted with the fiber material. The pretreatment agent comprises polymer P and may optionally further comprise components other than polymer P (other components).

[0033] 1.2.1 Polymer P

[0034] Polymer P comprises dicarboxylic acid units and diol units. Polymer P can be obtained, for example, by transesterification, direct polymerization, etc.

[0035] (Dicarboxylic acid unit)

[0036] The dicarboxylic acid unit constituting polymer P comprises at least 5 mol% and 30 mol% of at least one of the following units: a unit (unit X) derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and a unit (unit Y) derived from a tricarboxylic acid. In other words, the dicarboxylic acid unit constituting polymer P comprises one or both of units X and units Y totaling 5 mol% and 30 mol%, with the remainder consisting of dicarboxylic acid units other than units X and units Y. Preferably, the dicarboxylic acid unit constituting polymer P comprises 5 mol% and 20 mol% or less, more preferably 5 mol% and 15 mol% or less, and even more preferably 5 mol% and 12 mol% or less of units X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group. Alternatively, the dicarboxylic acid unit constituting polymer P preferably comprises 8 mol% and 20 mol% or less, more preferably 10 mol% and 20 mol% or less of units Y derived from a tricarboxylic acid. When the dicarboxylic acid unit constituting polymer P has unit X, said unit X is derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group. By making said unit X within the above-mentioned range, excellent water repellency can be imparted. The same applies to the case where the dicarboxylic acid unit constituting polymer P has a unit Y derived from a tricarboxylic acid.

[0037] In one embodiment, the polymer P has an anionic group comprising one or more selected from sulfonic acid, sulfonate, carboxylic acid, and carboxylate groups. The polymer P may also contain anionic groups other than these, such as one or more selected from sulfate, sulfate, phosphate, and phosphate groups.

[0038] In polymer P, the ratio of anionic groups other than units X and Y can be less than 30 mol% or 0 mol% in a total of 100 mol% of anionic groups.

[0039] Furthermore, "units derived from tricarboxylic acids" can be expressed as "units derived from dicarboxylic acids that additionally have one carboxylic acid group or carboxylate group." That is, in this application, "units derived from tricarboxylic acids" are exceptionally considered as a type of "dicarboxylic acid unit." On the other hand, in this application, "units derived from polycarboxylic acids with four or more members" are not considered as "dicarboxylic acid units."

[0040] The dicarboxylic acid unit constituting polymer P can be derived from an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid, preferably from an aromatic dicarboxylic acid. The aromatic dicarboxylic acid can be, for example, at least one selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, and p-hydroxybenzoic acid. When the dicarboxylic acid unit constituting polymer P includes units derived from one or both of terephthalic acid and isophthalic acid, superior properties are readily obtained. The aliphatic dicarboxylic acid can be, for example, at least one selected from succinic acid, sebacic acid, dodecanoic acid, maleic acid, and succinic acid. These dicarboxylic acids can be acid anhydrides or ester derivatives formed with lower alcohols or diols.

[0041] A dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group can be a dicarboxylic acid having a sulfonic acid group and / or a sulfonate group bonded to the various dicarboxylic acids described above. The sulfonate group can be, for example, a metal salt group such as a Li salt, Na salt, K salt, or Mg salt, or an amine salt group such as ammonia or triethanolamine. Alkali metal salt groups are particularly preferred, with Na salt groups being the most preferred. A dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group can be, for example, at least one selected from sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, their salts, their dimethyl esters, diethyl esters, diphenyl esters, and other ester derivatives thereof.

[0042] Tricarboxylic acids (dicarboxylic acids having one or both of a carboxylic acid group and a carboxylate group) can be substances having a carboxylic acid group and / or a carboxylate group bonded to the various dicarboxylic acids described above. In one embodiment, such tricarboxylic acids are intended to be free of a sulfonic acid group and a sulfonate group. The carboxylate group can be, for example, a metal salt group such as a Li salt, Na salt, K salt, or Mg salt, or an amine salt group such as ammonia or triethanolamine. Alkali metal salt groups are particularly preferred, with Na salt groups being the most preferred. As a tricarboxylic acid (a dicarboxylic acid containing a carboxylic acid group), for example, it can be at least one selected from trimellitic acid, pyromellitic acid, 1,2,3-benzenetricarboxylic acid, their salts, their dimethyl esters, diethyl esters, diphenyl esters, and other ester derivatives.

[0043] The dicarboxylic acid units constituting polymer P may, for example, include units derived from dicarboxylic acid p1 that do not have sulfonic acid groups and sulfonate groups and are not tricarboxylic acids, and units derived from dicarboxylic acid p2 that have one or both of sulfonic acid groups and sulfonate groups and are not tricarboxylic acids. Alternatively, the dicarboxylic acid units constituting polymer P may, for example, include units derived from dicarboxylic acid p1 that do not have sulfonic acid groups and sulfonate groups and are not tricarboxylic acids, and units derived from tricarboxylic acid p3 (a dicarboxylic acid having one or both of a carboxylic acid group and a carboxylate group). The carbon skeletons of dicarboxylic acid p1, dicarboxylic acid p2, and tricarboxylic acid p3 may be of the same or different types. The dicarboxylic acid unit constituting polymer P may, for example, include units derived from one or both of terephthalic acid and isophthalic acid, which are dicarboxylic acids p1 that do not have sulfonic acid groups and sulfonate groups and are not tricarboxylic acids; and may include units derived from sulfoisophthalic acid, which are dicarboxylic acids p2 that have one or both of sulfonic acid groups and sulfonate groups and are not tricarboxylic acids. Specific examples of tricarboxylic acid p3 are as described above.

[0044] The dicarboxylic acid units constituting polymer P can be, for example, units derived from dicarboxylic acids with a molecular weight of 100 or more and 300 or less. From the perspective of imparting good water repellency, the aforementioned molecular weight can be 100 or more, and from the perspective of the water solubility of polymer P, it can be 300 or less.

[0045] (Polycarboxylic acid units other than dicarboxylic acid units)

[0046] For polymer P, as structural units, in addition to the dicarboxylic acid mentioned above, it may also include units derived from 4- to 6-membered polycarboxylic acids such as tetracarboxylic acid, pentacarboxylic acid, and hexacarboxylic acid. The molecular weight of the polycarboxylic acids other than the dicarboxylic acid can be 100 or more and 400 or less in one embodiment. In polymer P, the proportion of dicarboxylic acid units in the total polycarboxylic acid units can, for example, be 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 in the total polycarboxylic acid units can, for example, be 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.

[0047] (Diol unit)

[0048] The diol units constituting polymer P are derived from diols with a molecular weight of 48 or more and 900 or less. The molecular weight of this diol is preferably 60 or more and 600 or less, more preferably 60 or more and 300 or less, and even more preferably 60 or more and 200 or less. If the molecular weight of the diol is too low, polymer P cannot achieve sufficient water solubility, posing a risk of decreased stability in the bath. On the other hand, if the molecular weight is too high, polymer P will have excessively high water solubility, which may adversely affect its water-repellent properties. In the case of aromatic diols, sufficient water solubility cannot be achieved, posing a risk of decreased stability in the bath.

[0049] In one embodiment, the diol unit may not have an anionic group.

[0050] The diol unit constituting polymer P can be derived from aliphatic diols or aromatic diols, and more preferably from diols containing aliphatic sites, particularly aliphatic diols. Examples of aliphatic diols include alkylene glycols and polyalkylene glycols. The diol can be at least one selected from polyethylene glycol, ethylene glycol, alkylene glycols with 3 or more carbon atoms, neopentyl glycol, polypropylene glycol, Purronick (registered trademark) type surfactants (polymers having ethylene oxide-propylene oxide copolymer sites), and bisphenol A ethylene oxide adducts (diols having aromatic and aliphatic sites). Among these, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of 200 to 600, 1,4-butanediol, and neopentyl glycol are preferred.

[0051] (Polyhydroxy compound units other than diol units)

[0052] In polymer P, in addition to the diols mentioned above, structural units derived from hydroxyl compounds may also include, for example, units derived from 3- to 6-membered polyhydroxyl compounds such as triols, tetraols, pentaols, and hexaols. The molecular weight of the polyhydroxyl compounds other than diols may, in one embodiment, be 48 or more and 900 or less. In polymer P, the proportion of diol units in the total polyhydroxyl compound units may, for example, be 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 polyhydroxyl compound units other than diol units in the total polyhydroxyl compound units may, for example, be 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.

[0053] In polymer P, in addition to the diols mentioned above, diols with a molecular weight of more than 900 may also be included as structural units derived from hydroxyl compounds.

[0054] In one embodiment, from the perspective of water repellency, the proportion of units derived from hydroxyl compounds with a molecular weight greater than 900 in the hydroxyl compound units of polymer P is preferably less than 5% by mass, or may be 0% by mass. If the proportion of diols with a molecular weight greater than 900 is too high, the water solubility of polymer P will be too high, which may have an adverse effect on the water repellency.

[0055] (Weight-average molecular weight of polymer P)

[0056] There is no particular limitation on the weight-average molecular weight of polymer P. When the dicarboxylic acid units constituting polymer P include units derived from dicarboxylic acids having one or both of sulfonic acid groups and sulfonate groups, the weight-average molecular weight of polymer P can be, for example, 2000 or more and 80000 or less, or 5000 or more and 70000 or less. When the dicarboxylic acid units constituting polymer P include units derived from tricarboxylic acids, the weight-average molecular weight of polymer P can be, for example, 2000 or more and 80000 or less, or 2000 or more and 20000 or less. When the weight-average molecular weight of polymer P is within such a range, the water repellency of the fiber product can be further improved. It should be noted that in this application, "weight-average molecular weight" is determined by size exclusion chromatography using an instrument: HLC-8120 (manufactured by Tosoh Corporation), a column: TSK-GEL Super AWM-H (manufactured by Tosoh Corporation), and a mobile phase of 10 mM LiBr-DMF, with polystyrene as the standard.

[0057] (The intramolecular ratio of dicarboxylic acid units in polymer P)

[0058] 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.

[0059] 1.2.2 Components other than polymers

[0060] The pretreatment agent may contain components other than polymer P. These components, other than polymer P, may include water, organic solvents, surfactants, etc.

[0061] 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, isopropanol, ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.

[0062] There are no particular limitations on the surfactant; it can be any known surfactant. For example, it can be at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0063] Anionic surfactants may be, for example, at least one selected from the following: sulfates, phosphates, or salts thereof of alkylene oxide adducts of aliphatic alcohols (the aliphatic alcohols having 1 to 22 carbon atoms); sulfates, phosphates, or salts thereof of polyalkylene glycols obtained from alkylene oxides having 2 to 4 carbon atoms; sulfates, phosphates, or salts thereof of mono- or polystyrene-based alkylene oxide adducts; sulfates, phosphates, or salts thereof of mono- or polystyrene-based alkylene oxide adducts (the alkyl group having 1 to 22 carbon atoms); alkylbenzenesulfonic acids (the alkyl group having 8 to 22 carbon atoms) or their salts; alkyl sulfonic acids (the alkyl group having 8 to 22 carbon atoms) or their salts; α-olefin sulfonic acids (the α-olefin fatty acids having 8 to 22 carbon atoms and the alkyl group having 1 to 12 carbon atoms) or their salts. For example, the salt can be selected from at least one of alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts.

[0064] Nonionic surfactants may be, for example, at least one selected from the following: alkylene oxide adducts of aliphatic alcohols (the aliphatic alcohols having 1 to 22 carbon atoms) or fatty acid esters of the fatty acids thereof (the fatty acids having 8 to 24 carbon atoms); polyalkylene glycols or fatty acid esters of the fatty acids thereof (the fatty acids having 8 to 24 carbon atoms) obtained from alkylene oxides having 2 to 4 carbon atoms; alkylene oxide adducts of mono- or polystyrene-modified phenols or fatty acid esters of the fatty acids thereof (the fatty acids having 8 to 24 carbon atoms); and fatty acid esters of alkylene oxide adducts of mono- or polystyrene-modified alkyl (alkyl groups having 1 to 22 carbon atoms) phenols (the fatty acids having 8 to 24 carbon atoms).

[0065] The cationic surfactant may be, for example, a quaternary ammonium surfactant selected from at least one of the following: 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 monoalkylamine or dialkylamine with a quaternizing agent; or an alkylpyridinium salt. The long-chain alkyl group of the aforementioned trialkylamine may have, for example, 6 to 24 carbon atoms, and the remaining alkyl group of the aforementioned trialkylamine may have, for example, 1 to 5 carbon atoms. The alkyl group of the aforementioned monoalkylamine or dialkylamine may have, for example, 6 to 24 carbon atoms. The aforementioned alkylene oxide may, for example, be an alkylene oxide having 2 to 4 carbon atoms, and the molar number of additions may, for example, be 2 to 50. The aforementioned quaternizing agent may, for example, be at least one selected from a haloalkane having 1 to 5 carbon atoms and a dialkyl sulfate having 1 to 5 carbon atoms. The alkyl group of the aforementioned alkylpyridinium salt may, for example, have 3 to 24 carbon atoms.

[0066] Amphoteric surfactants can be, for example, at least one selected from alkyl amine oxides, alanine derivatives, imidazoline betaines, amide betaines, and acetate betaines. Specifically, examples include long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazoline betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amide propyl dimethylaminoacetic acid betaine.

[0067] 1.2.3 Polymer P content

[0068] There is no particular limitation on the amount of polymer P contained in the pretreatment agent. For example, the ratio (mass percentage) of polymer P contained in the pretreatment agent can be 0.1 to 70% by mass, or 0.5 to 50% by mass.

[0069] 1.3 Contact Method

[0070] In one embodiment of the method for manufacturing a water-repellent fiber article, the polymer P (a pretreatment agent containing polymer P) can be brought into contact with the fiber material (the material to be treated) to adhere to the fiber material.

[0071] When the pretreatment agent contains water, it is preferable to dry it after it is applied to the fibrous material in order to remove the water.

[0072] There are no particular limitations on the method of contacting the polymer P (a pretreatment agent containing polymer P) with the fiber material.

[0073] For example, as a continuous contact method (continuous process), pad dyeing, spraying, and coating processes can be cited. As an intermittent process, immersion processing can be cited.

[0074] In the continuous process, the fiber material is continuously fed into an impregnation device (a device that allows the pretreatment agent to be in continuous contact with the fiber material) filled with a pretreatment agent containing polymer P (or a pretreatment liquid that has been further diluted), and after the pretreatment liquid has impregnated the fiber material, the unwanted pretreatment liquid is removed.

[0075] On the other hand, intermittent methods include, for example, the steps of immersing the fibrous material in a pretreatment solution and removing the solvent remaining in the treated fibrous material.

[0076] In continuous processes, rolling mills, kiss-roller application devices, gravure coating machine application devices, spray application devices, foam application devices, and coating application devices are preferred, with rolling mills being particularly preferred. Continuous processes are especially suitable when the fibrous material is in the form of fabrics or cloth.

[0077] There are no particular restrictions on the drying method; it can be either dry heat or wet heat. There are also no particular restrictions on the drying machine; however, hot air dryers, tenter frame machines, and other spreading dryers are preferred.

[0078] In the intermittent dyeing method, various intermittent dyeing machines can be used, such as cotton yarn dyeing machines, package yarn dyeing machines, warp beam dyeing machines, liquid flow dyeing machines, airflow dyeing machines, drum dyeing machines, rope dyeing machines, washing dyeing machines, and package yarn dyeing machines. The intermittent method is preferred when the fibrous material is not in the form of fabric, such as loose fibers, wool tops, rovings, skeins, silk bundles, or yarns, or when knitted fabrics are not suitable for continuous dyeing methods.

[0079] As a drying method, hot air dryers such as yarn dryers, warp beam dryers, drum dryers, and high-frequency dryers can be used.

[0080] When using a continuous method for treatment or a batch method for contacting a treatment agent containing polymer P, the concentration, temperature, and other treatment conditions of the treatment solution can be appropriately adjusted to take into account various conditions such as purpose and performance.

[0081] There are no particular restrictions on drying temperature; for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, a heat treatment at 100-180°C for about 10 seconds to 5 minutes can be performed.

[0082] Additionally, at least one of the treatment solutions used for dyeing, soaping, and / or cleaning the fiber materials may contain the aforementioned pretreatment agent, allowing it to contact the fiber material. Two or three of the dyeing solution, soaping solution, and cleaning solution may contain polymer P. From the perspective of minimizing color variations in polyester-dyed fiber products, addition to the soaping solution and / or cleaning solution, particularly the soaping solution and cleaning solution, is more preferable.

[0083] For example, the use of polyester fibers as fiber materials will be explained.

[0084] 1.3.1 Staining treatment

[0085] As a method for contacting polymer P, one example is using a dyeing solution containing polymer P during the dyeing process of polyester fibers.

[0086] 1.3.1.1 Polyester fibers

[0087] Polyester fibers that are subject to dyeing treatment can be any fibers containing polyester fibers. Polyester fibers can be, for example, one or two of the following fibers: polyester fibers formed from homopolymers or copolymers thereof selected from at least one of polyethylene terephthalate, propylene terephthalate, trimethylene terephthalate, and butylene terephthalate; or composite fibers selected from at least one of blends, interweavings, and cross-knittings of polyester fibers with other synthetic fibers and natural fibers. The form of polyester fibers can be, for example, at least one of yarns, knitted fabrics, woven fabrics, and nonwoven fabrics. Polyester fibers are preferably refined.

[0088] 1.3.1.2 Dyeing solution

[0089] The staining solution may contain polymer P. In addition, the staining solution may contain other components besides polymer P.

[0090] (Amount of polymer P contained in the staining solution)

[0091] There is no particular limitation on the amount of polymer P contained in the staining solution. Preferably, the amount of polymer P contained in the staining solution is 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.

[0092] (Components other than polymer P)

[0093] Other than polymer P, components may include water, organic solvents, and surfactants. Additionally, the staining solution may contain acids, chelating agents, etc., for pH adjustment. Details regarding organic solvents, surfactants, etc., are as described above.

[0094] From the perspective of better leveling and staining properties, the staining solution preferably contains at least one surfactant selected from anionic surfactants and nonionic surfactants.

[0095] There is no particular limitation on the amount of surfactants, etc., contained in the dyeing solution. However, considering better leveling and dyeing properties, the amount of surfactants contained in the dyeing solution is preferably 0.001 g / L or more and 25 g / L or less, more preferably 0.015 g / L or more and 6.0 g / L or less.

[0096] 1.3.1.3 Other conditions in staining treatment

[0097] There are no particular restrictions on other conditions in the dyeing process; conditions that enable the dyeing of the polyester fibers using the dyeing solution described above can be adopted. For example, the following conditions can be cited.

[0098] (Liquor ratio in dyeing process)

[0099] The ratio of polyester fiber to dyeing solution varies depending on the target performance, etc. On a mass basis, it can be, for example, 1:3 to 1:30, preferably 1:5 to 1:25, and more preferably 1:5 to 1:20.

[0100] (dye)

[0101] Any dye capable of coloring polyester fibers will suffice. Disperse dyes are suitable, for example. The amount of dye used can be appropriately selected; for example, it can be above 0.001% owf and below 20% owf.

[0102] (Dyeing machine)

[0103] There are no particular restrictions on the dyeing machines used in the dyeing process; conventional dyeing machines can be used. Examples include liquid flow dyeing machines, rope dyeing machines, roll dyeing machines, beam dyeing machines, package dyeing machines, Obermere dyeing machines, and high-pressure jet dyeing machines.

[0104] (Staining temperature and staining time)

[0105] The polyester fibers are dyed by contacting the dyeing solution with the dyeing machine described above. The dyeing temperature and time can be maintained under the same conditions as before. For example, the dyeing solution can be heated to approximately 40-60°C for about 50-80 minutes. If faster dyeing is desired, the temperature can be slowly increased over about 30-50 minutes, and the dyeing can be performed at 120-140°C (preferably 125-135°C) for about 0-90 minutes, preferably 30-60 minutes.

[0106] 1.3.2 Soap washing treatment

[0107] As a method of contacting polymer P, one example is to perform a soaping treatment on dyed polyester fibers in the same bath or a different bath as the dyeing solution.

[0108] 1.3.2.1 Soap Wash

[0109] Washing liquid may contain polymer P. In addition, washing liquid may contain other components besides polymer P.

[0110] (Amount of polymer P contained in the soap solution)

[0111] There is no particular limitation on the amount of polymer P contained in the soaping solution. Preferably, the amount of polymer P contained in the soaping solution is 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.

[0112] (Components other than polymer P)

[0113] Other than polymer P, known components used in soaping processes include alkalis, reducing agents, etc. The soaping solution may also contain water, organic solvents, surfactants, etc. These may be derived from the dyeing solution. Details regarding organic solvents, surfactants, etc., are as described above. Additionally, the soaping solution may contain acids, chelating agents, etc., for adjusting the pH value.

[0114] The reducing agent can be, for example, at least one selected from dithionite, sodium dithionite, thiourea dioxide, and reducing sugars (D-glucose, D-xylose, etc.). In this case, the pH adjuster can be any alkaline substance, such as caustic soda or soda ash. From the perspective of soaping effect, when using at least one selected from dithionite, sodium dithionite, thiourea dioxide, and reducing sugars as the reducing agent, caustic soda is preferred as the pH adjuster. Alternatively, from the same perspective, when using at least one selected from dithionite, sodium dithionite, and thiourea dioxide as the reducing agent, soda ash can be used as the pH adjuster.

[0115] The reducing agent can be at least one sulfinic acid or its salt selected from, for example, sodium hydroxymethanesulfinate, etc., and the pH adjuster can be any substance as long as it is an acidic substance such as acetic acid or formic acid.

[0116] The reducing agent is preferably selected from at least one of dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethanesulfinate, and more preferably from at least one of dithionite, sodium dithionite, and thiourea dioxide. Combining such a reducing agent with the aforementioned polymer P readily and significantly improves the fastness.

[0117] 1.3.2.2 Other conditions in soaping treatment

[0118] There are no particular restrictions on other conditions in the soaping process; conditions that enable the aforementioned soaping solution to soap the aforementioned polyester fibers can be adopted. For example, the following conditions can be cited.

[0119] (Bath ratio in soap washing treatment)

[0120] The ratio of polyester fiber to soap solution varies depending on the target performance, and can 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.

[0121] (Soap washing temperature and soap washing time)

[0122] The temperature for soaping can be the typical temperature used in dyeing processes, i.e., the range of 60~140°C. However, considering the reduction in various physical properties and hand feel of the fiber products, a temperature of 70~100°C is preferred, and more preferably, a range of 70~90°C. The soaping time can be, for example, 5~60 minutes. From the perspective of ensuring thorough soaping and suppressing the reduction in various physical properties of the fiber products, a time of 10~30 minutes is preferred.

[0123] 1.3.3 Two-bath, two-stage treatment (2-bath, 2-stage method)

[0124] As an example of the method of performing the above-mentioned dyeing and soaping treatments in different baths (2 baths) (2 bath 2 stage method), the following first method can be listed.

[0125] The first method is to discard the dyeing solution after dyeing and re-prepare a soaping solution (soap bath) for soaping treatment.

[0126] 1.3.4 Same-bath treatment (1-bath 2-stage method)

[0127] As an example of conducting the dyeing and soaping processes in the same bath (1 bath), specifically, in a 1-bath 2-stage method, after the dyeing process, instead of completely draining the dyeing solution, a portion or all of the remaining dyeing solution is added to the solution for soaping. By conducting the dyeing and soaping processes in the same bath (1 bath), water and energy can be saved.

[0128] In a co-bath treatment, for example, a soaping solution can be prepared using 20% ​​to 100% by volume, 50% to 100% by volume, 70% to 100% by volume, or 90% to 100% by volume of the dyeing solution. If the dyeing solution is not discharged after the dyeing treatment, 100% by volume of the dyeing solution is used as the soaping solution.

[0129] As specific methods for performing dyeing and soaping treatments in the same bath (1 bath), examples such as the second and third methods described below can be cited. Furthermore, in the manufacturing method of the present invention, as in the second method described below, even if the dyeing solution used in the dyeing treatment contains polymer P, the dyeing treatment of polyester fibers can be appropriately performed using the dyeing solution.

[0130] The second method involves using a dyeing solution containing polymer P in the dyeing process, where at least a portion of the polymer P contained in the dyeing solution is used as at least a portion of the polymer P contained in the soaping solution. More specifically, for example, this can be achieved by dyeing with a dyeing solution containing polymer P, then adding a pH adjuster and a reducing agent to the dyeing solution (dyeing bath) to prepare a soaping solution (soaping bath), followed by soaping treatment.

[0131] The third method involves preparing a soaping solution by adding at least polymer P to the dyeing solution (dyeing bath) after dyeing treatment and then performing soaping treatment. More specifically, for example, the following method is used: For the dyeing solution (dyeing bath) after dyeing treatment, a pH adjuster and a reducing agent are added along with polymer P to prepare a soaping solution (soaping bath) for soaping treatment.

[0132] For either the second or third method described above, there are no particular restrictions on the timing of adding pH adjusters and reducing agents to the staining solution after staining treatment. Preferably, the pH adjuster and reducing agent are added to the staining solution during cooling after staining treatment, or after cooling to the temperature for soaping treatment (preferably after cooling to the temperature for soaping treatment). The timing of adding polymer P is the same for the third method. Furthermore, in the second method, after staining treatment using a staining solution containing polymer P, polymer P may or may not be added to the staining solution. In the second method, if polymer P is further added to the staining solution after staining treatment, the timing can be the same as described above.

[0133] 1.3.5 Cleaning Treatment

[0134] As a method for contacting polymer P, one or both of the following cleaning treatments can be used: hot water washing and water washing of polyester fibers after soaping. Here, the cleaning solution used in the cleaning process may contain the aforementioned polymer P. Alternatively, the cleaning solution may contain components other than polymer P.

[0135] (Amount of polymer P contained in the cleaning solution)

[0136] There is no particular limitation on the amount of polymer P contained in the cleaning solution. Preferably, the amount of polymer P contained in the cleaning solution is 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.

[0137] (Components other than polymer P)

[0138] The cleaning solution may contain components other than polymer P. Examples of components other than polymer P include well-known components used in hot water washing and / or water washing processes (pH adjusters, etc.).

[0139] (Other conditions during the cleaning process)

[0140] There are no particular restrictions on other conditions in the cleaning process; conditions that allow for hot water cleaning and / or water washing of the polyester fibers using the aforementioned cleaning solution may be adopted. For example, the following conditions may be cited.

[0141] (Liquor ratio in cleaning process)

[0142] The ratio of polyester fiber to cleaning solution varies depending on the target performance, and can 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.

[0143] (Cleaning temperature and cleaning time)

[0144] The cleaning temperature can be a typical processing temperature, for example, in the range of 20~100°C, preferably in the range of 30~90°C. The cleaning time can be, for example, 2~60 minutes. Considering the need for thorough cleaning and improving the quality of various physical properties of the fiber products, 5~30 minutes is preferred.

[0145] 1.4 Supplement

[0146] Furthermore, in the above description, the case where the "dicarboxylic acid unit" constituting polymer P exceptionally includes "a unit derived from a tricarboxylic acid (a unit derived from a dicarboxylic acid having one or both of a carboxylic acid group and a carboxylate group)" has been explained. On the other hand, assuming that "dicarboxylic acid unit" and "unit derived from a tricarboxylic acid" are distinguished, the polymer P of this disclosure may also be represented as one or both of the following polyester copolymers P1 and P2. That is, the technology of the present invention also has an aspect of a method for manufacturing a water-repellent fiber article using one or both of the following polyester copolymers P1 and P2.

[0147] (Polyester copolymer P1)

[0148] The polyester copolymer P1 comprises a dicarboxylic acid unit p1-1 and a diol unit p1-2. The dicarboxylic acid unit p1-1 comprises 5 mol% to 30 mol% of a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group. The diol unit p1-2 is derived from a diol with a molecular weight of 48 to 900. The intramolecular content of the dicarboxylic acid unit p1-1 in the polyester copolymer P1 is 50% to 75% by mass.

[0149] (Polyester copolymer P2)

[0150] Polyester copolymer P2 comprises dicarboxylic acid unit p2-1, diol unit p2-2, and tricarboxylic acid unit p2-3. The tricarboxylic acid unit p2-3 accounts for more than 5 mol% and less than 30 mol% of the total of dicarboxylic acid unit p2-1 and the tricarboxylic acid unit p2-3. The diol unit p2-2 is derived from a diol with a molecular weight of more than 48 and less than 900. The intramolecular content ratio of the total of dicarboxylic acid unit p2-1 and tricarboxylic acid unit p2-3 in polyester copolymer P2 is more than 50% by mass and less than 75% by mass.

[0151] In the polyester copolymer P2, the dicarboxylic acid unit p2-1 may or may not contain unit X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group. The total proportion of unit X and unit Y derived from a tricarboxylic acid in the dicarboxylic acid unit p2-1 may be more than 5 mol% and less than 30 mol%.

[0152] 2. Water-repellent treatment

[0153] In one embodiment of the method for manufacturing a water-repellent fiber article, the fiber material, after the above-mentioned pretreatment (after contact with a polyester copolymer having anionic groups), is brought into contact with a non-fluorinated water-repellent component. For example, a water-repellent treatment agent containing a non-fluorinated water-repellent component is prepared, and the water-repellent treatment agent is brought into contact with the fiber material.

[0154] 2.1 Water-repellent agent

[0155] Water-repellent agents contain non-fluorinated water-repellent components and may further contain other components (other components) in any way.

[0156] 2.1.1 Non-fluorinated water-repellent components

[0157] The non-fluorinated water-repellent component may be at least one of acrylic compounds, organosilicon compounds, wax compounds, carbamate compounds, and dendritic macromolecular compounds. From the perspective of durable water repellency, the non-fluorinated water-repellent component is preferably one or both of acrylic compounds and organosilicon compounds, more preferably organosilicon compounds.

[0158] (Acrylic compounds)

[0159] Acrylic compounds, for example, have structural units derived from (meth)acrylate monomers (hereinafter also referred to as "(A1) components") represented by the following general formula (A1). Acrylic compounds may further have structural units derived from compounds represented by the following general formula (A2) (hereinafter also referred to as "(A2) components"). In addition, in this application, "(meth)acrylate" refers to "acrylate" or its corresponding "methacrylate", and the same applies to "(meth)acrylic acid", "(meth)acrylamide", etc.

[0160]

[0161] In formula (A1), R 1 For hydrogen or methyl, R 2 It is a monovalent hydrocarbon group that can have 12 to 30 carbon atoms and can have substituents.

[0162]

[0163] In equation (A2), R 11 For hydrogen or methyl, R 12 It is a divalent hydrocarbon group with 1 to 6 carbon atoms, Z is an ester or amide group, and W is -CO-R. 13 (R) 13 The group is represented by 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).

[0164]

[0165] The above-mentioned component (A1) comprises a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have substituents. This hydrocarbon group may be linear or branched, saturated or unsaturated, and may have an alicyclic or aromatic cyclic structure. From the perspective of water repellency, a linear chain is preferred, and a linear alkyl chain is more preferred. In this case, the water repellency is even better. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has substituents, one or more of the following substituents can be selected: hydroxyl, amino, carboxyl, epoxy, isocyanate, terminal isocyanate, and (meth)acryloyloxy. In the above general formula (A-1), R... 2 Preferably, it contains unsubstituted hydrocarbon groups. Using unsubstituted hydrocarbon groups results in superior initial water repellency. Additionally, it contributes to improved durable water repellency.

[0166] The number of carbon atoms in the aforementioned hydrocarbon group is preferably 12 to 24, more preferably 12 to 22. When the number of carbon atoms is within this range, the water repellency and hand feel become particularly excellent. As a hydrocarbon group, a straight-chain alkyl group with 18 to 22 carbon atoms is particularly preferred.

[0167] As an ingredient in (A1) above, examples include at least one selected from stearyl methacrylate, cetyl methacrylate, lauryl methacrylate, myristyl methacrylate, pentadecyl methacrylate, heptadecanyl methacrylate, nonadecanyl methacrylate, eicosyl methacrylate, dodecyl methacrylate, and dodecyl methacrylate.

[0168] The above-mentioned (A1) component may have at least one functional group selected from hydroxyl, amino, carboxyl, epoxy, and isocyanate groups capable of reacting with a crosslinking agent. In R 2 When a portion of the component has functional groups capable of reacting with a crosslinking agent, durable water repellency can be further improved. Isocyanate groups can form capped isocyanate groups protected by a capping agent. Furthermore, when the aforementioned component (A1) contains amino groups, the hand feel can be further improved.

[0169] The above-mentioned component (A1) is preferably a monofunctional (meth)acrylate monomer having one polymerizable unsaturated group per molecule.

[0170] The above-mentioned (A1) ingredient can be used alone or in combination of two or more.

[0171] In the above formula (A2), R 12 It can be a straight chain or a branched chain, it can be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and it can also have an alicyclic cyclic structure.

[0172] In the above formula (A2), when Z is an ester group, R 12 Preferably, it is a hydrocarbon group with 2 to 4 carbon atoms, and W is a group represented by -NH-CO-NH2 or a group represented by the above formula (W1). When Z is an amide group, R 12 Preferably, it is a hydrocarbon group with 2 to 4 carbon atoms, and W is -CO-R. 13 The group represented is preferably R. 13 The number of carbon atoms is 1 to 2.

[0173] There are no particular limitations on the components listed in (A2) above, and examples include diacetone acrylamide, 2-methacrylate [2-(2-oxo-2-imidazolyl)ethyl] ester, and N-[2-(2-oxoimidazolyl-3-yl)ethyl]methacrylamide. Among these, considering durability and water repellency, diacetone acrylamide and 2-methacrylate [2-(2-oxo-2-imidazolyl)ethyl] ester are preferred as components in (A2).

[0174] The above-mentioned (A2) ingredient can be used alone or in combination of two or more.

[0175] Regarding the content ratio of structural units derived from component (A1) to structural units derived from component (A2) in acrylic compounds, the mass ratio of component (A1) to component (A2) (A1) / (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. If (A1) / (A2) is within the above range, the durability and water resistance are improved.

[0176] The total mass of the (A1) component and the (A2) component, relative to the total amount of the monomer components constituting the acrylic compound, is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass.

[0177] In terms of peel strength, acrylic compounds may contain at least one monomer (A3) of vinyl chloride and vinylidene chloride (hereinafter also referred to as "(A3) component") as monomer components, in addition to component (A1) and optional component (A2).

[0178] Considering the need to maintain the feel of the fiber product, the preferred component (A3) is vinyl chloride.

[0179] The mass of the compounded component (A3), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, considering water repellency, durable water repellency, and peel strength. Regarding the mass of the compounded component (A3), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, considering water repellency, durable water repellency, and hand feel, is preferably 100 parts by mass or less, 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.

[0180] Acrylic compounds, in view of improving their emulsification stability in the composition during and after emulsion polymerization or dispersion polymerization, preferably contain, in addition to component (A1) and optional component (A2), at least one of the following reactive emulsifiers (A4) (hereinafter also referred to as "(A4) component") as monomer components: compounds with an HLB of 7 to 18 and represented by the following general formula (A4-1), compounds with an HLB of 7 to 18 and represented by the following general formula (A4-2), and compounds with an HLB of 7 to 18 formed by adding an epoxide having 2 to 4 carbon atoms to an oil having hydroxyl and polymerizable unsaturated groups (A4-3).

[0181]

[0182] In equation (A4-1), R 3 X is hydrogen or methyl, X is a straight-chain or branched alkylene group having 1 to 6 carbon atoms, and Y is... 1 It is a divalent group containing an alkylene oxide with 2 to 4 carbon atoms.

[0183]

[0184] In equation (A4-2), R 4 Y is a monovalent unsaturated hydrocarbon group with 13-17 carbon atoms and a polymerizable unsaturated group. 2 It is a divalent group containing an alkylene oxide with 2 to 4 carbon atoms.

[0185] In this application, "reactive emulsifier" refers to an emulsifying dispersant with free radical reactivity, that is, a surfactant with one or more polymerizable unsaturated groups in its molecule, which can copolymerize with monomers such as (meth)acrylates.

[0186] In addition, the "HLB" of reactive emulsifiers refers to the calculated HLB value obtained by the Griffin method, treating the ethylene oxide group in the reactive emulsifier as a hydrophilic group and all other groups as lipophilic groups. The HLB of reactive emulsifiers can be 7.0~16.0, 7.0~15.5, 7.0~15.0, or 7.0~14.5. When the HLB deviates from this range, there is a tendency for the initial Bundesmann water repellency and the Bundesmann water repellency to decrease after wear.

[0187] HLB = 20 × [(Molecular weight of hydrophilic groups in the reactive emulsifier) ​​ / (Molecular weight of the reactive emulsifier)]

[0188] The HLB values ​​of the compounds (A4-1) to (A4-3) described above are 7 to 18, and preferably 9 to 15, considering the emulsification stability (hereinafter referred to as emulsification stability) of the acrylic compounds in the emulsion polymerization or dispersion polymerization and in the post-polymerization composition. Furthermore, considering the storage stability of the water-repellent composition containing non-fluorinated water-repellent components, it is more preferable to use two or more reactive emulsifiers (A4) with different HLB values ​​within the above range in combination.

[0189] In the above general formula (A4-1), R 3 X is hydrogen or methyl; methyl is more preferred from the perspective of copolymerization with components (A1) and / or (A2). X is a straight-chain or branched alkylene group having 1 to 6 carbon atoms; straight-chain alkylene group having 2 to 3 carbon atoms is more preferred from the perspective of emulsification stability of acrylic compounds. Y1 It is a divalent group containing an alkylene oxide with 2 to 4 carbon atoms. Regarding Y... 1 The types, combinations, and number of alkylene oxides in the structure can be appropriately selected in a manner that achieves the aforementioned HLB range. Furthermore, when there are two or more alkylene oxides, they can have block addition or random addition structures.

[0190] As for the compound represented by the above general formula (A4-1), the compound represented by the following general formula (A4-1-1) is preferred.

[0191]

[0192] In formula (A4-1-1), R 3 X is hydrogen or methyl, X is a straight-chain or branched alkylene group having 1 to 6 carbon atoms, and A is a hydrogen or methyl group. 1 O is an alkylene oxide with 2 to 4 carbon atoms, and m can be appropriately selected in a way that achieves the above-mentioned HLB range. Specifically, it is preferably an integer from 1 to 80. When m is 2 or more, m A 1 O can be the same or different.

[0193] In the compounds represented by the above general formula (A4-1-1), R 3 X is hydrogen or methyl; methyl is more preferred from the perspective of copolymerization with components (A1) and / or (A2). X is a straight-chain or branched alkylene group having 1 to 6 carbon atoms; a straight-chain alkylene group having 2 to 3 carbon atoms is more preferred from the perspective of emulsification stability of acrylic compounds. A 1 O is an alkylene oxide with 2 to 4 carbon atoms. Regarding A... 1 The type and combination of O, and the value of m, can be appropriately selected in a way that achieves the aforementioned HLB range. Considering the emulsification stability of acrylic compounds, m is preferably an integer from 1 to 80, more preferably an integer from 1 to 60. When m is 2 or more, m A 1 O can be the same or different. Additionally, in A... 1 When there are two or more types of O, they can have block addition structures or random addition structures.

[0194] The reactive emulsifier represented by the above general formula (A4-1-1) can be obtained by conventionally known methods without particular limitation. In addition, it can be readily obtained from commercially available products, such as "Radium PD-420", "Radium PD-430", and "Radium PD-450" manufactured by Kao Corporation.

[0195] In the above general formula (A4-2), R 4It is a monovalent unsaturated hydrocarbon group with 13 to 17 carbon atoms, possessing a polymerizable unsaturated group. Examples of such unsaturated hydrocarbon groups include tridecylenyl, tridecyldienyl, tetradecylenyl, tetradecyldienyl, pentadecylenyl, pentadecyldienyl, pentadecyltrienyl, heptadecanylenyl, heptadecanyldienyl, and heptadecanyltrienyl. Considering the emulsification stability of acrylic compounds, R is preferred. 4 More preferably, it is a monovalent unsaturated hydrocarbon group with 14 to 16 carbon atoms.

[0196] Y 2 It is a divalent group containing an alkylene oxide with 2 to 4 carbon atoms. Regarding Y... 2 The types, combinations, and number of alkylene oxides in the compound can be appropriately selected to achieve the aforementioned HLB range. Furthermore, when there are two or more alkylene oxides, they can have block addition or random addition structures. From the perspective of emulsification stability of acrylic compounds, ethylene oxides are more preferred.

[0197] As for the compound represented by the above general formula (A4-2), the compound represented by the following general formula (A4-2-1) is preferred.

[0198]

[0199] In equation (A4-2-1), R 4 A is a monovalent unsaturated hydrocarbon group with 13 to 17 carbon atoms that has a polymerizable unsaturated group. 2 O is an alkylene oxide with 2 to 4 carbon atoms, and n can be appropriately selected in a way that achieves the above-mentioned HLB range. Specifically, it is preferably an integer from 1 to 50. When n is 2 or more, n A 2 O can be the same or different.

[0200] R in the compound represented by the above general formula (A4-2-1) 4 This indicates that R in the above general formula (A4-2) is different. 4 The same group.

[0201] A 2 O is an alkylene oxide with 2 to 4 carbon atoms. Considering the emulsification stability of acrylic compounds, regarding A... 2 The type and combination of O, and the value of n, can be appropriately selected in a way that achieves the aforementioned HLB range. Considering the emulsification stability of acrylic compounds, A is preferred. 2 O is an ethylene oxide, and n is preferably an integer from 1 to 50, more preferably an integer from 5 to 20, and even more preferably an integer from 8 to 14. When n is 2 or more, n A 2 O can be the same or different. Additionally, in A...2 When there are two or more types of O, they can have block addition structures or random addition structures.

[0202] The reactive emulsifier represented by the above general formula (A4-2-1) can be synthesized, for example, by adding an epoxide to a phenol having the corresponding unsaturated hydrocarbon group, but is not limited thereto. For example, it can be synthesized by adding a specified amount of epoxide to a base catalyst such as sodium hydroxide or potassium hydroxide under pressure at 120-170°C.

[0203] Among the phenols with corresponding unsaturated hydrocarbon groups mentioned above, in addition to industrially manufactured pure products or mixtures, there are also substances that exist as pure products or mixtures extracted or purified from plants, etc. For example, examples include 3-[8(Z),11(Z),14-pentadecantrienyl]phenol, 3-[8(Z),11(Z)-pentadecanadienyl]phenol, 3-[8(Z)-pentadecanenyl]phenol, 3-[11(Z)-pentadecanenyl]phenol, etc., which are extracted from cashew nut shells, etc.

[0204] Compound (A4-3) is formed by adding an alkylene oxide with 2 to 4 carbon atoms to an oil with an HLB of 7 to 18 and having hydroxyl and polymerizable unsaturated groups. Examples of oils having hydroxyl and polymerizable unsaturated groups include monoglycerides or diglycerides of fatty acids containing hydroxyunsaturated fatty acids (palmitoic 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, trans-ricinoleic acid, 2-hydroxytetraenoic acid, etc.). From the perspective of emulsifying stability of acrylic compounds, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid are preferred; alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) with 2 to 4 carbon atoms are more preferred; and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the molar number of epoxides added can be appropriately selected to achieve the aforementioned HLB range. Considering the emulsification stability of acrylic compounds, 20 to 50 molars is more preferred, and 25 to 45 molars is even more preferred. In addition, when there are two or more epoxides, they can have block addition structures or random addition structures.

[0205] Compound (A4-3) can be synthesized, for example, by adding an epoxide to an oil containing hydroxyl and polymerizable unsaturated groups, but is not limited thereto. For example, it can be synthesized by adding a specified amount of an epoxide to a triglyceride of fatty acids containing ricinoleic acid, i.e., castor oil, under pressure and at 120-170°C using a base catalyst such as sodium hydroxide or potassium hydroxide.

[0206] Regarding the composition ratio of the monomers of the above-mentioned (A4) component in the acrylic compound, from the viewpoint of improving water repellency and emulsification stability of the acrylic compound in the composition during emulsion polymerization or dispersion polymerization and after polymerization, the total amount of the monomer components constituting the acrylic compound is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass.

[0207] In order to improve durable water repellency, in addition to component (A1) and optional component (A2), acrylic compounds may also contain at least one second (meth)acrylate monomer (A5) (hereinafter also referred to as "A5 component") selected from the monomers represented by general formula (A5-1), the monomers represented by general formula (A5-2), the monomers represented by general formula (A5-3) and the monomers represented by general formula (A5-4) as monomer components.

[0208]

[0209] In formula (A5-1), R 5 For hydrogen or methyl, R 6 It is a monovalent chain hydrocarbon group having 1 to 11 carbon atoms and having at least one functional group selected from hydroxyl, amino, carboxyl, epoxy, isocyanate, and (meth)acryloyloxy. The number of (meth)acryloyloxy groups within the molecule is 2 or less.

[0210]

[0211] In formula (A5-2), R 7 For hydrogen or methyl, R 8 It is a monovalent cyclic hydrocarbon group that can have 1 to 11 carbon atoms and may have substituents.

[0212]

[0213] In formula (A5-3), R 9 It is a monovalent chain hydrocarbon group with 1 to 4 unsubstituted carbon atoms.

[0214]

[0215] In formula (A5-4), R 10 It is hydrogen or methyl, p is an integer greater than 2, S is an organic group with a (p+1) valence, and T is a monovalent organic group with a polymerizable unsaturated group.

[0216] The monomer described above (A5-1) is a (meth)acrylate monomer having a monovalent chain hydrocarbon group with 1 to 11 carbon atoms in the ester moiety, wherein the monovalent chain hydrocarbon group with 1 to 11 carbon atoms has at least one functional group selected from hydroxyl, amino, carboxyl, epoxy, isocyanate, and (meth)acryloyloxy. From the viewpoint of being able to react with the crosslinking agent, the monovalent chain hydrocarbon group with 1 to 11 carbon atoms preferably has at least one functional group selected from hydroxyl, amino, carboxyl, epoxy, and isocyanate. When an acrylic compound containing a monomer of (A5-1) having groups capable of reacting with these crosslinking agents is used to treat fiber products together with a crosslinking agent, the durable water repellency can be improved while maintaining the hand feel of the obtained fiber product. The isocyanate group can be a capped isocyanate group protected by a capping agent.

[0217] The aforementioned chain-like hydrocarbon groups can be straight-chain or branched-chain, and can be saturated or unsaturated. Furthermore, in addition to the aforementioned functional groups, the chain-like hydrocarbon groups may further have substituents. From the perspective of improving durable water repellency, straight-chain and / or saturated hydrocarbon groups are preferred.

[0218] Specific monomers for (A5-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers can be used alone or in combination of two or more. From the perspective of improving durable water repellency, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred. Furthermore, from the perspective of improving the feel, dimethylaminoethyl (meth)acrylate is preferred.

[0219] The mass of the compounded component (A5-1), relative to the total mass of the compounded components (A1) and (A2) of 100 parts by mass, is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water repellency. The mass of the compounded component (A5-1), relative to the total mass of the compounded components (A1) and (A2) of 100 parts by mass, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the perspective of water repellency.

[0220] The monomers described above (A5-2) are (meth)acrylate monomers having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester moiety. Examples of cyclic hydrocarbon groups include isobornyl, cyclohexyl, and dicyclopentyl. These cyclic hydrocarbon groups may have substituents such as alkyl groups. Where the substituent is a hydrocarbon group, the hydrocarbon group whose total number of carbon atoms (substituent and cyclic hydrocarbon group) is 11 or less is selected. Furthermore, from the perspective of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to the ester bond. The cyclic hydrocarbon group can be alicyclic or aromatic; in the case of an alicyclic group, it can be a saturated or unsaturated hydrocarbon group. Specific monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentyl (meth)acrylate. These monomers can be used alone or in combination of two or more. Among these, considering the ability to improve durable water repellency, isobornyl methacrylate and cyclohexyl methacrylate are preferred, with isobornyl methacrylate being more preferred.

[0221] The mass of the compounded component (A5-2), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water repellency. The mass of the compounded component (A5-2), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the perspective of water repellency.

[0222] The monomers described above (A5-3) are methacrylate monomers in which a monovalent chain hydrocarbon group with 1 to 4 unsubstituted carbon atoms is directly bonded to the ester bond of the ester moiety. Preferably, the chain hydrocarbon group with 1 to 4 carbon atoms is a straight-chain hydrocarbon group with 1 to 2 carbon atoms or a branched chain hydrocarbon group with 3 to 4 carbon atoms. Examples of the chain hydrocarbon group with 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate. These monomers can be used alone or in combination of two or more. From the perspective of improving durable water repellency, methyl methacrylate, isopropyl methacrylate, and tert-butyl methacrylate are preferred, and methyl methacrylate is more preferred.

[0223] The mass of the compounded component (A5-3), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water repellency. The mass of the compounded component (A5-3), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the perspective of water repellency.

[0224] The monomer in (A5-4) above is a (meth)acrylate monomer having three or more polymerizable unsaturated groups per molecule. Preferably, T in the above general formula (A5-4) is a (meth)acryloyloxy group, or a multifunctional (meth)acrylate monomer having three or more (meth)acryloyloxy groups per molecule. In formula (A5-4), the p Ts can be the same or different. Specific compounds include, for example, ethoxylated isocyanurate triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. These monomers can be used alone or in combination of two or more. Among them, tetramethylolmethane tetraacrylate and ethoxylated isocyanurate triacrylate are more preferred from the perspective of improving durable water repellency.

[0225] The mass of the compounded component (A5-4), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water repellency. The mass of the compounded component (A5-4), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the perspective of water repellency.

[0226] The total composition ratio of the monomers of the above-mentioned (A5) component in the acrylic compound, from the perspective of water repellency and feel, is preferably 1 to 30% by mass relative to the total amount of monomer components constituting the acrylic compound, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.

[0227] The mass of the compounded component (A5), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water repellency. The mass of the compounded component (A5), relative to the total mass of the compounded components (A1) and (A2) for 100 parts by mass, is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the perspective of water repellency.

[0228] For acrylic compounds, in addition to component (A1) and optional component (A2), a monofunctional monomer (A6) capable of copolymerizing with them may be contained (hereinafter also referred to as "(A6) component"), to a extent that does not impair the effects of the present invention.

[0229] As a component (A6), examples include (meth)acryloylmorpholine, (meth)acrylates with hydrocarbon groups other than those listed in (A1), (A2), and (A5), (meth)acrylic acid, fumarate, maleate, fumaric acid, maleic acid, (meth)acrylamide, N-hydroxymethylacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers other than those in component (A3) that are not fluorinated. It should be noted that (meth)acrylates with hydrocarbon groups other than those in components (A1), (A2), and (A5) may have substituents such as vinyl, hydroxyl, amino, epoxy, isocyanate, or terminal isocyanate groups on the hydrocarbon group, or substituents other than quaternary ammonium groups that can react with crosslinking agents, and may also have ether bonds, ester bonds, amide bonds, or carbamate bonds. Examples of (meth)acrylates other than components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate. Among these, (meth)acryloylmorpholine is more preferred in terms of improving the peel strength of the obtained fibrous article to the coating.

[0230] The mass of the compounded component (A6), relative to 100 parts by mass of the combined components (A1) and (A2), is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, from the perspective of water resistance. The mass of the monomer of the compounded component (A6), relative to 100 parts by mass of the combined components (A1) and (A2), is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, from the perspective of water repellency.

[0231] Acrylic compounds, from the perspective of improving durable water repellency, preferably have at least one functional group selected from hydroxyl, amino, carboxyl, epoxy, and isocyanate groups that can react with crosslinking agents. The isocyanate group can form a capped isocyanate group protected by a capping agent. Furthermore, from the perspective of improving texture, acrylic compounds preferably have an amino group.

[0232] The weight-average molecular weight of acrylic compounds is preferably 30,000 or higher. When the weight-average molecular weight is 30,000 or higher, the water repellency tends to be further improved. Furthermore, the weight-average molecular weight of acrylic compounds is more preferably 50,000 or higher. In this case, the hydrophobicity can be more fully utilized. The upper limit of the weight-average molecular weight of acrylic compounds is preferably around 5 million.

[0233] The weight-average molecular weight of acrylic compounds refers to the value determined using a GPC apparatus (Tosoh Corporation's GPC "HLC-8020") at a column temperature of 40°C and a flow rate of 1.0 ml / min, using tetrahydrofuran as the eluent, and converted to standard polystyrene. It should be noted that the column used is a combination of three Tosoh Corporation's commercially available columns, TSK-GELG5000HHR, G4000HHR, and G3000HHR.

[0234] The melt viscosity of acrylic compounds at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, there is a tendency to maintain a good hand feel. Furthermore, when the melt viscosity of acrylic compounds is 1000 Pa·s or less, when acrylic compounds are emulsified or dispersed to form water-repellent compositions, the precipitation or sedimentation of acrylic compounds can be suppressed, thus tending to maintain good storage stability of the water-repellent composition. It should be noted that the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, sufficient water repellency can be achieved, and the hand feel is also superior.

[0235] "Melt viscosity at 105°C" refers to the viscosity measured using a high-performance flow tester (e.g., Shimadzu CFT-500). 1g of a non-fluorinated polymer is added to a barrel equipped with a die (10mm in length, 1mm in diameter), held at 105°C for 6 minutes, and then 100kg·f / cm² is applied using a plunger. 2 The viscosity was measured under load.

[0236] (Organosilicon compounds)

[0237] Organosilicon compounds include, for example, at least one of organosilicon resins and silicone oils. Among such organosilicon compounds, organosilicon resins are preferred from the perspective of water repellency. Organosilicon compounds can be used alone or in combination of two or more.

[0238] Organosilicon resins can also be organopolysiloxanes containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as constituent components, which are solid at 25°C and have a three-dimensional structure. M, D, T, and Q represent (R)₃SiO₂, respectively. 0.5 Unit, (R)2SiO unit, R”SiO 1.5 Unit and SiO2 unit. "R" represents a monovalent aliphatic hydrocarbon group with 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group with 6 to 15 carbon atoms.

[0239] Silicone resins are commonly referred to as MQ resins, MT resins, or MDT resins, and sometimes also have a part indicating MDQ, MTQ, or MDTQ.

[0240] Organosilicon resins can be obtained alone or in the form of a solution formed by dissolving them in a suitable solvent. Examples of solvents include, for example, low molecular weight methyl polysiloxanes, decamethylcyclopentasiloxanes, octamethylcyclotetrasiloxanes, n-hexane, isopropanol, dichloromethane, 1,1,1-trichloroethane, and mixtures of these solvents.

[0241] Examples of solutions containing organosilicon resins include KF7312J (a mixture of trimethylsilyl polysiloxane and decamethylcyclopentasiloxane in a mass ratio of 50:50), KF7312F (a mixture of trimethylsilyl polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane in a mass ratio of 50:50), and KF7312L (a mixture of trimethylsilyl polysiloxane and low-viscosity methyl polysiloxane in a mass ratio of 50:50), all commercially available from Shin-Etsu Chemical Co., Ltd.

[0242] Examples of individual silicone resins include MQ-1600 solid Resin (a trimethylsilyl polysiloxane) and MQ-1640 Flake Resin (a mixture of trimethylsilyl polysiloxane and polypropylsilsesquioxane) commercially available from Toray Dow Corning Co., Ltd. These commercially available products contain trimethylsilyl polysiloxanes, including MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0243] Silicone oil is a linear organopolysiloxane, which may have organic groups on at least one of its side chains and terminals. As such silicone oils, silicone oils similar to hydrophobic silicone oils and functionalized silicone oils can be used, for example, common silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrosiloxane; and modified silicone oils such as amino-modified silicone oil, epoxy-modified silicone oil, methanol-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, and higher aliphatic amide-modified silicone oil.

[0244] As amino-modified silicone oils, compounds having at least one organic group comprising an amino and / or imino group in the side chain and terminal portion of an organopolysiloxane can be listed. Examples of such organic groups include the organic group represented by -R-NH2 and the organic group represented by -R-NH-R'-NH2. Examples of R and R' include divalent groups such as ethylidene and propylene. Some or all of the amino and / or imino groups can be pre-terminated amino and / or imino groups. Pre-terminated amino and / or imino groups can be obtained, for example, by treating the amino and / or imino groups with a capping agent. Examples of capping agents include, for example, fatty acids having 2 to 22 carbon atoms, anhydrides of fatty acids having 2 to 22 carbon atoms, acyl halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

[0245] In terms of water repellency, the functional group equivalent of amino-modified silicone oil is preferably 100~20000 g / mol, more preferably 150~12000 g / mol, and even more preferably 200~4000 g / mol.

[0246] The amino-modified silicone oil is preferably liquid at 25°C. The kinematic viscosity of the amino-modified silicone oil at 25°C is preferably 10~100,000 mm⁻¹. 2 / s, more preferably 10~30,000 mm 2 / s, further preferably 10~5,000mm 2 / s. Kinematic viscosity at 25°C greater than 100,000 mm³ / s. 2 At a viscosity of 1 / s, the viscosity is too high, which tends to reduce operability. The kinematic viscosity at 25°C refers to the value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0247] As an amino-modified silicone oil, it is readily available as a commercially available product. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, KF-8021 (all manufactured by Shin-Etsu Chemical Co., Ltd., trade name), TSF-4709, XF42-B1989 (manufactured by Momentive Advanced Materials Japan Contract Co., Ltd., trade name), BY16-872, SF-8417, BY16-853U, BY16-892 (all manufactured by Toray Dow Corning Co., Ltd., trade name), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and WACKER (registered trademark) FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicones), etc.

[0248] In addition, 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 Toray Dow Corning Co., Ltd., trade name: methanol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methylhydrosilicone oil), and X-22-715 (Shin-Etsu Chemical...). Products manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: Advanced fatty acid ester modified silicone oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: Dimethyl silicone oil), SF8416 (manufactured by Toray Dow Corning Co., Ltd. (trade name: Alkyl modified silicone oil), SH203 (manufactured by Toray Dow Corning Co., Ltd. (trade name: Alkyl aralkyl modified silicone oil), SF8410 (manufactured by Toray Dow Corning Co., Ltd. (trade name: Polyether modified silicone oil), etc.

[0249] Organosilicon compounds can be organically modified organosilicones represented by the following general formula (1). It should be noted that in the following general formula (1), each structural unit can be a block, a random, or arranged alternately.

[0250]

[0251] In equation (1), R 20 R 21 and R 22 Each is independently a hydrogen atom, methyl, ethyl, or an alkoxy group having 1 to 4 carbon atoms, R 23 R is a hydrocarbon group having an aromatic ring with 8 to 40 carbon atoms, or an alkyl group having 3 to 40 carbon atoms. 30 R 31 R 32 R 33 R 34 and R 35Each of the following groups of R is independently a hydrogen atom, methyl, ethyl, alkoxy group with 1 to 4 carbon atoms, hydrocarbon group with 8 to 40 carbon atoms having an aromatic ring, or alkyl group with 3 to 40 carbon atoms, where a is an integer greater than or equal to 0, b is an integer greater than or equal to 1, (a+b) is 10 to 200, and when a is greater than or equal to 2, multiple R groups exist. 20 and R 21 Each can be the same or different. When b is 2 or more, there are multiple R. 22 and R 23 They can be the same or different.

[0252] In organosilicon modification, the alkoxy groups with 1 to 4 carbon atoms can be linear or branched. Examples of alkoxy groups with 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. From the perspective of ease of industrial manufacture and availability, R is preferred. 20 R 21 and R 22 Each is independently a hydrogen atom or a methyl group, more preferably a methyl group.

[0253] Examples of hydrocarbon groups having an aromatic ring and having 8 to 40 carbon atoms include aralkyl groups having 8 to 40 carbon atoms, groups represented by the following general formulas (2) or (3).

[0254]

[0255] In equation (2), R 40 R is an alkylene group with 2 to 6 carbon atoms. 41 It is a single bond or an alkylene group with 1 to 4 carbon atoms, where c is an integer from 0 to 3. When c is 2 or 3, multiple R groups exist. 41 They can be the same or different.

[0256] The aforementioned alkylene groups can be either straight-chain or branched-chain.

[0257]

[0258] In equation (3), R 42 R is an alkylene group with 2 to 6 carbon atoms. 43 It is a single bond or an alkylene group with 1 to 4 carbon atoms, where d is an integer from 0 to 3. When d is 2 or 3, multiple R groups exist. 43 They can be the same or different.

[0259] The aforementioned alkylene groups can be either straight-chain or branched-chain.

[0260] Examples of aryl alkyl groups with 8 to 40 carbon atoms include phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, and naphthylethyl. Among these, phenylethyl and phenylpropyl are preferred from the perspective of ease of industrial manufacture and availability.

[0261] Among the groups represented by the above general formula (2), considering their ease of industrial manufacture and availability, R 40 Preferably, it is an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, more preferably 0.

[0262] Among the groups represented by the above general formula (3), considering their ease of industrial manufacture and availability, R 42 Preferably, it is an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, more preferably 0.

[0263] As for the hydrocarbon group having an aromatic ring with 8 to 40 carbon atoms, from the perspective of easy industrial manufacture and easy availability, the aralkyl group having 8 to 40 carbon atoms and the group represented by the general formula (2) are preferred. From the perspective of improving water repellency, the aralkyl group having 8 to 40 carbon atoms is more preferred.

[0264] The alkyl groups with 3 to 40 carbon atoms can be straight-chain or branched-chain. Examples of alkyl groups with 3 to 40 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, behenyl, hexadecyl, octadecyl, triacontyl, and tridodecyl. From the perspective of improving water repellency, alkyl groups with 12 to 36 carbon atoms are preferred, and alkyl groups with 16 to 34 carbon atoms are more preferred. Furthermore, alkyl groups with fewer carbon atoms tend to have excellent chalk-scratch resistance. Conversely, alkyl groups with more carbon atoms tend to have excellent water repellency. However, if the number of carbon atoms exceeds 40, the stability of the dispersion tends to decrease. Furthermore, when the number of carbon atoms is less than 3, the water repellency tends to deteriorate.

[0265] In organically modified organosilicon, R 30 R 31 R 32 R 33 R 34 and R 35 Each of the following groups is independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group with 1 to 4 carbon atoms, a hydrocarbon group with 8 to 40 carbon atoms having an aromatic ring, or an alkyl group with 3 to 40 carbon atoms. From the perspective of ease of industrial manufacture and availability, R is preferred. 30 R 31 R 32 R33 R 34 and R 35 Each of the components is preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, with a more preferred methyl group.

[0266] In organically modified silicones, 'a' is an integer greater than or equal to 0. Considering ease of industrial manufacture, availability, and superior peel strength, 'a' is preferably 40 or less, and more preferably 30 or less.

[0267] In organically modified organosilicon, (a+b) is 10 to 200. From the perspective of ease of industrial manufacture and availability, (a+b) is preferably 20 to 100, more preferably 40 to 60. If (a+b) is within the above range, the manufacture and processing of the organosilicon itself tend to become easier.

[0268] Organically modified organosilicones can be synthesized using methods known in the art. For example, organically modified organosilicones can be obtained by hydrosilylation of an aromatic compound having a vinyl group and / or an α-olefin with an organosilicon having a SiH group.

[0269] Examples of organosilicones with SiH groups include, for instance, methylhydrosilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrosiloxane. Among these, methylhydrosilicones are preferred from the perspective of ease of industrial manufacture and availability.

[0270] The above-mentioned aromatic compounds containing vinyl groups are R that constitute the general formula (1) above. 23 Compounds derived from hydrocarbon groups having an aromatic ring with 8 to 40 carbon atoms. Examples of vinyl aromatic compounds include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tris(phenylethyl)-phenyl ether, allyl-tris(2-phenylpropyl)phenyl ether, etc.

[0271] The above-mentioned α-olefins are the R that constitutes the above general formula (1). 23 Compounds derived from alkyl groups having 3 to 40 carbon atoms. Examples of α-olefins include, for instance, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-octadecene, 1-hexadecene (C26), 1-octadecene (C28), 1-triacene (C30), and 1-tridodecene (C32), which have 3 to 40 carbon atoms.

[0272] The above-mentioned hydrosilylation reaction can be carried out by reacting the above-mentioned vinyl aromatic compound and the above-mentioned α-olefin with the above-mentioned organosilicon having SiH group in a stepwise or one-time manner, if necessary, in the presence of a catalyst.

[0273] The amounts of organosilicon compounds with SiH groups, aromatic compounds with vinyl groups, and α-olefins used in the hydrosilylation reaction can be appropriately selected based on the equivalent SiH group or number-average molecular weight of the organosilicon compounds with SiH groups.

[0274] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum chloride (IV).

[0275] The reaction conditions for hydrosilylation are not particularly limited and can be adjusted appropriately. The reaction temperature is, for example, 10~200℃, preferably 50~150℃. The reaction time, for example, at a reaction temperature of 50~150℃, can be set to 3~12 hours.

[0276] Furthermore, the hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction can also be carried out without a solvent, but a solvent can also be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0277] As a non-fluorinated water-repellent component, considering water repellency and chalk scratch resistance, it is preferable to use both the aforementioned acrylic compound and the aforementioned organosilicon compound. The mass ratio of the acrylic compound (α) to the organosilicon compound (β) is not particularly limited. For example, when the organosilicon compound (β) is an organosilicon resin, if the total mass of the acrylic compound (α) and the organosilicon compound (β) is considered to be 100 parts by mass, the organosilicon compound (β) may account for 1 to 99 parts by mass. Preferably, it is 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, and even more preferably 15 to 95 parts by mass. By maintaining the proportion of the organosilicon compound (β) within this range, excellent water repellency after abrasion and Bundesmann water repellency are achieved. Alternatively, if the organosilicon compound (β) is an organically modified organosilicon, if the total mass of the acrylic compound (α) and the organosilicon compound (β) is considered to be 100 parts by mass, the organosilicon compound (β) may account for 10 to 90 parts by mass. Preferably, the proportion is 10 to 80 parts by weight, more preferably 15 to 70 parts by weight, and even more preferably 20 to 60 parts by weight. By setting the proportion of the organosilicon compound (β) within this range, excellent water repellency is achieved, and in addition, chalk marks are less likely to occur.

[0278] (Wax compounds)

[0279] The wax compound is, for example, at least one selected from paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and plant waxes and mineral waxes, with paraffin wax being preferred in terms of water repellency, durable water repellency and feel.

[0280] Wax compounds can be, for example, one or both of n-alkanes and n-olefins. From the perspectives of water repellency, durable water repellency, and feel, n-alkanes are preferred wax compounds.

[0281] Examples of n-alkanes include, for instance, at least one selected from trisane, tetrasane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, triacontane, trisane-dodecane, trisane-tetradecane, trisane-pentadecane, trisane-pentadecane, and hexadecane. From the perspectives of water repellency, durable water repellency, and feel, triacontane, trisane, and trisane-dodecane are preferred.

[0282] Examples of n-olefins include at least one selected from 1-eicosene, 1-docoene, 1-tricocephane, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-octacosene, 29-carbosene, triacosene, 31-carbosene, 32-carbosene, 33-carbosene, 34-carbosene, 35-carbosene, and 36-carbosene. From the perspectives of water repellency, durable water repellency, and feel, n-olefins are preferably at least one selected from triacosene, 31-carbosene, and 32-carbosene.

[0283] There is no particular limitation on the number of carbon atoms in wax compounds, which can be 20 to 60. However, considering water repellency, durable water repellency, and feel, 25 to 45 is preferred.

[0284] There are no particular restrictions on the weight average molecular weight of wax compounds, which can be 300 to 850. Considering water repellency, durable water repellency and feel, a weight average molecular weight of 300 to 700 is preferred.

[0285] Considering good and durable water repellency, especially good and durable water repellency against cotton, the melting point of the wax compound is preferably 35~90℃, more preferably 40~85℃, even more preferably 45~80℃, and even more preferably 50~75℃. The melting point of the wax compound refers to the value determined using the same method as JIS K2235-1991 6.3.

[0286] The penetration of wax compounds is not particularly limited; for example, it can be 30 or less. However, considering 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 wax compounds is not particularly limited; for example, it can be 0.1 or more, or 1 or more. The penetration of wax compounds refers to the value measured using the same method as JIS K2235-1991 6.4.

[0287] (Carbamate compounds)

[0288] Carbamate compounds are, for example, reaction products of aliphatic polyisocyanate derivatives, long-chain active hydrogen compounds, cationic active hydrogen compounds, and acid compounds. More specifically, for example, they can be...

[0289] (U1) Aliphatic polyisocyanate derivatives with an average isocyanate group number of 2 or more, (U2) Long-chain active hydrogen compounds that simultaneously possess a hydrocarbon group with 12 or more but less than 30 carbon atoms and an active hydrogen group. (U3) Cationic active hydrogen compounds that simultaneously possess both active hydrogen groups and cationic groups and (U4) Acidic compounds that can form salts with cationic groups The reaction product. Here, the concentration of the aforementioned hydrocarbon group can be 30% or more and 85% or less. Furthermore, the aforementioned aliphatic polyisocyanate derivative may include isocyanurate derivatives of aliphatic polyisocyanates. Moreover, in the aforementioned cationic active hydrogen compound, the aforementioned cationic group can be a tertiary amino group, the aforementioned active hydrogen group can be a hydroxyl group, and the aforementioned cationic active hydrogen compound can be a cationic active hydrogen compound having two or more hydroxyl groups per molecule. When the carbamate compound is a reaction product obtained using a long-chain active hydrogen compound and the concentration of the hydrocarbon group is in a specified proportion, the water repellency tends to become excellent. Furthermore, when the carbamate compound is a reaction product obtained using a cationic active hydrogen compound, for example, the affinity with fibers is improved, thereby easily improving wash durability.

[0290] Examples of aliphatic polyisocyanates constituting aliphatic polyisocyanate derivatives (U1) include, for example, hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. Furthermore, in this application, "aliphatic polyisocyanate" includes the concept of alicyclic polyisocyanates.

[0291] Examples of alicyclic polyisocyanates include, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate) or mixtures thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (H6XDI), bis(isocyanatomethyl)norbornene (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, and other alicyclic diisocyanates.

[0292] The aliphatic polyisocyanate is preferably one or two of hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter referred to as bis(isocyanatomethyl)cyclohexane), more preferably hexamethylene diisocyanate.

[0293] Examples of aliphatic polyisocyanate derivatives include, for example, polymers of the aforementioned aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazine dione derivatives), pentamers, heptamers, etc.), urethane derivatives (e.g., urethane derivatives generated by the reaction of the aforementioned aliphatic polyisocyanates with a monohydric alcohol or a dihydric alcohol), and polyol derivatives (e.g., polyol derivatives (alcohol adducts, preferably trihydric alcohols) generated by the reaction of the aforementioned aliphatic polyisocyanates with a trihydric alcohol (e.g., trimethylolpropane, etc.). Hydroxymethylpropane adducts, etc.), biuret derivatives (e.g., biuret derivatives generated by the reaction of the above-mentioned aliphatic polyisocyanates with water or amines), urea derivatives (e.g., urea derivatives generated by the reaction of the above-mentioned aliphatic polyisocyanates with diamines), oxadiazine trione derivatives (e.g., oxadiazine triones generated by the reaction of the above-mentioned aliphatic polyisocyanates with carbon dioxide), carbodiimide derivatives (carbodiimide derivatives generated by the decarbonation condensation reaction of the above-mentioned aliphatic polyisocyanates), urea dione derivatives, urea ketone imine derivatives, etc.

[0294] The aliphatic polyisocyanate derivative is preferably at least one of isocyanurate derivatives, trimethylolpropane adducts, urethane derivatives, and biuret derivatives, more preferably isocyanurate derivatives. If the aliphatic polyisocyanate derivative includes isocyanurate derivatives, the feel becomes better.

[0295] The aliphatic polyisocyanate derivative is more preferably at least one of the following: isocyanurate derivative of hexamethylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, biuret derivative of hexamethylene diisocyanate, and isocyanurate derivative of bis(isocyanate methyl)cyclohexane, and more preferably isocyanurate derivative of hexamethylene diisocyanate.

[0296] Aliphatic polyisocyanate derivatives may be used alone or in combination of two or more. Preferred examples include the use of hexamethylene diisocyanate isocyanurate derivatives alone, or the use of hexamethylene diisocyanate isocyanurate derivatives in combination with at least one selected from bis(isocyanate-methyl)cyclohexane, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, and biuret derivative of hexamethylene diisocyanate. In this case, the proportion of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more, preferably 70 parts by mass or more, and for example, 85 parts by mass or less, relative to the total amount of at least one selected from bis(isocyanatomethyl)cyclohexane isocyanurate derivative, trimethylolpropane adduct of hexamethylene diisocyanate, urethane derivative of hexamethylene diisocyanate, and biuret derivative of hexamethylene diisocyanate, which is 100 parts by mass.

[0297] Aliphatic polyisocyanate derivatives can be manufactured using known methods.

[0298] The average isocyanate group number of the aliphatic polyisocyanate derivative is 2 or more, preferably 2.5 or more, more preferably 2.9 or more, and, for example, 3.8 or less. When the above-mentioned average isocyanate group number is above the lower limit, the water repellency can be further improved. It should be noted that the average isocyanate group number is calculated by the following formula (1) from the isocyanate group concentration A, the solids concentration B, and the number average molecular weight C measured by gel permeation chromatography under the following apparatus and conditions. In addition, when two or more aliphatic polyisocyanate derivatives are used, the above-mentioned average isocyanate group number is calculated by the weight ratio of the aliphatic polyisocyanate derivatives and their average number of isocyanate functional groups.

[0299] Average number of isocyanate functional groups = A / B×C / 42.02 (1)

[0300] In the formula, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solids concentration, and C represents the number-average molecular weight.

[0301] (Determination conditions for number-average molecular weight)

[0302] Device: HLC-8220GPC (Tosoh Manufacturing)

[0303] Column: Connect TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (Tosoh) in series.

[0304] Detector: Differential refractometer

[0305] Injection volume: 100μL

[0306] Eluent: Tetrahydrofuran

[0307] Flow rate: 0.8 mL / min

[0308] Temperature: 40℃

[0309] Calibration curve: Standard polyethylene oxide (Tosoh, trade name: TSK standard polyethylene oxide) in the range of 106~22450.

[0310] Long-chain active hydrogen compounds simultaneously possess hydrocarbon groups with 12 or more but less than 30 carbon atoms and active hydrogen groups that can react with aliphatic polyisocyanate derivatives.

[0311] The hydrocarbon group having 12 or more and 30 or less carbon atoms can be, for example, a straight-chain or branched-chain saturated hydrocarbon group (e.g., alkyl, etc.) having 12 or more and 30 or less carbon atoms, or a straight-chain or branched-chain unsaturated hydrocarbon group (e.g., alkenyl, etc.) having 12 or more and 30 or less carbon atoms.

[0312] The active hydrogen group can be, for example, a hydroxyl group.

[0313] For such long-chain active hydrogen compounds that simultaneously possess hydrocarbon groups and active hydrogen groups, for example, they can be at least one of the following: active hydrogen compounds containing straight-chain saturated hydrocarbon groups, active hydrogen compounds containing branched-chain saturated hydrocarbon groups, active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups, and active hydrogen compounds containing branched-chain unsaturated hydrocarbon groups.

[0314] Active hydrogen compounds containing straight-chain saturated hydrocarbon groups are active hydrogen compounds containing straight-chain saturated hydrocarbon groups with 12 or more but less than 30 carbon atoms. Examples include alcohols containing straight-chain saturated hydrocarbon groups such as n-tetranol, n-tetradecanool, n-pentadecanol, n-hexadecanool, n-heptadecanool, n-octadecanool (stearyl alcohol), n-nonadecanol, and eicosanool, as well as sorbitol esters containing straight-chain saturated hydrocarbon groups such as sorbitol tristearate.

[0315] Active hydrogen compounds containing branched chain saturated hydrocarbon groups are active hydrogen compounds containing branched chain saturated hydrocarbon groups with 12 or more but less than 30 carbon atoms. Examples include isomearithol, isocetyl alcohol, isostearyl alcohol, isoetiol, and isoeicosyl alcohol, which contain branched chain saturated hydrocarbon groups.

[0316] Active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups are active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups with 12 or more but less than 30 carbon atoms. Examples include tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, eicosenoyl alcohol, docosenoyl alcohol, tetradecenyl alcohol, hexadecenyl alcohol, octadecenyl alcohol, and other alcohols containing straight-chain unsaturated hydrocarbon groups.

[0317] Active hydrogen compounds containing branched chain unsaturated hydrocarbon groups are active hydrogen compounds containing branched chain unsaturated hydrocarbon groups with 12 or more but less than 30 carbon atoms, such as phytol.

[0318] Long-chain active hydrogen compounds are preferably one or two of the following: active hydrogen compounds containing straight-chain saturated hydrocarbon groups and active hydrogen compounds containing straight-chain unsaturated hydrocarbon groups. Long-chain active hydrogen compounds can be used alone or in combination of two or more.

[0319] When using a long-chain active hydrogen compound alone, it is preferable to use an active hydrogen compound containing a straight-chain saturated hydrocarbon group alone, more preferably to use an alcohol containing a straight-chain saturated hydrocarbon group alone, and even more preferably to use stearyl alcohol alone. When using two or more long-chain active hydrogen compounds together, it is preferable to use an active hydrogen compound containing a straight-chain saturated hydrocarbon group and an active hydrogen compound containing a straight-chain unsaturated hydrocarbon group together, more preferably to use an alcohol containing a straight-chain saturated hydrocarbon group and an alcohol containing a straight-chain unsaturated hydrocarbon group together, or to use an alcohol containing a straight-chain saturated hydrocarbon group, an anhydrous sorbitol ester containing a straight-chain saturated hydrocarbon group, and an alcohol containing a straight-chain unsaturated hydrocarbon group together.

[0320] When using alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of the alcohol containing the straight-chain saturated hydrocarbon group relative to the total amount of the alcohols containing the straight-chain saturated hydrocarbon group and the alcohols containing the straight-chain unsaturated hydrocarbon group is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, and more preferably 70 parts by mass or more. Furthermore, the proportion of the alcohol containing the straight-chain unsaturated hydrocarbon group relative to the total amount of the alcohols containing the straight-chain saturated hydrocarbon group and the alcohols containing the straight-chain unsaturated hydrocarbon group is, for example, 60 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less. If the proportion of the alcohol containing the straight-chain saturated hydrocarbon group is above the above lower limit, the crystallinity of the hydrocarbon group is improved, resulting in improved water repellency.

[0321] When using alcohols containing straight-chain saturated hydrocarbon groups, dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups, the proportion of alcohols containing straight-chain saturated hydrocarbon groups relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups, dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 30 parts by mass or more, and also, for example, 60 parts by mass or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups, dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups. Furthermore, the proportion of dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups, dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 20 parts by mass or more, and also, for example, 50 parts by mass or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups, dehydrated sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups. In addition, the proportion of alcohols containing straight-chain unsaturated hydrocarbon groups is, for example, 10 parts by mass or more, and for example, 20 parts by mass or less, relative to the total amount of alcohols containing straight-chain saturated hydrocarbon groups, sorbitol esters containing straight-chain saturated hydrocarbon groups, and alcohols containing straight-chain unsaturated hydrocarbon groups, which is 100 parts by mass.

[0322] When using two or more long-chain active hydrogen compounds, it is even more preferable to use alcohols containing straight-chain saturated hydrocarbon groups and alcohols containing straight-chain unsaturated hydrocarbon groups, and it is particularly preferable to use stearyl alcohol and oleyl alcohol.

[0323] Cationic active hydrogen compounds possess both active hydrogen groups and cationic groups. Cationic active hydrogen compounds can be used alone or in combination with two or more types.

[0324] As described above, the active hydrogen group is an active hydrogen group that can react with aliphatic polyisocyanate derivatives, such as hydroxyl groups. Cationic active hydrogen compounds preferably have two or more hydroxyl groups per molecule. Additionally, cationic groups can be, for example, tertiary amino groups. That is, for cationic active hydrogen compounds, it is preferable that each molecule simultaneously has two or more hydroxyl groups as active hydrogen groups and a tertiary amino group as a cationic group. More preferably, each molecule of a cationic active hydrogen compound simultaneously has two hydroxyl groups as active hydrogen groups and a tertiary amino group as a cationic group. Based on such cationic active hydrogen compounds, good dispersibility in water can be imparted, and furthermore, cationic groups with affinity for fibers can be introduced, thus improving wash durability.

[0325] Examples of such cationic active hydrogen compounds include alkyl diethanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, with N-methyldiethanolamine being a preferred example.

[0326] The acid compound is a compound that can form a salt with a cationic group. Examples of acid compounds include one or both organic and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, or malic acid, with acetic acid or lactic acid being preferred, and acetic acid being more preferred. Examples of inorganic acids include hydrochloric acid, sulfuric acid, or phosphoric acid, with hydrochloric acid being preferred. The acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid can be volatilized by heat treatment, thereby reducing its ionicity and increasing its water resistance, thus improving water repellency. Furthermore, by volatilizing the acid through heat treatment, the cationic groups can be easily adsorbed onto the fibers, thereby improving wash durability. Two or more acid compounds can be used alone or in combination.

[0327] By reacting the aforementioned aliphatic polyisocyanate derivative, long-chain active hydrogen compound, cationic active hydrogen compound, and acid compound, a carbamate compound can be obtained as the reaction product. To react the aliphatic polyisocyanate derivative, long-chain active hydrogen compound, cationic active hydrogen compound, and acid compound, firstly, a long-chain active hydrogen compound is mixed into the aliphatic polyisocyanate derivative, and the aliphatic polyisocyanate derivative reacts with the long-chain active hydrogen compound. At this time, for example, when the average isocyanate group number of the aliphatic polyisocyanate isocyanurate derivative is 3, the long-chain active hydrogen compound is preferably mixed in such a manner that two isocyanate groups in the aliphatic polyisocyanate isocyanurate derivative are modified by the long-chain active hydrogen compound into hydrocarbon groups with 12 or more and 30 or fewer carbon atoms, one isocyanate group remains in the aliphatic polyisocyanate isocyanurate derivative, and no unreacted aliphatic polyisocyanate isocyanurate derivative remains. Specifically, a long-chain active hydrogen compound is blended into an aliphatic polyisocyanate derivative such that the equivalence 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 also, for example, 2.0 or less. As a result, the molecule-terminus 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) consists of a hydrocarbon group and an isocyanate group having 12 or more and 30 or less carbon atoms.

[0328] The above reaction was carried out under a nitrogen atmosphere. Regarding the reaction conditions, the reaction temperature was, for example, 70°C or higher and 120°C or lower, and the reaction time was 1 hour or higher and 6 hours or lower. The reaction was continued until the isocyanate concentration of the first intermediate product reached a predetermined calculated value. The isocyanate concentration could be determined using a potentiometric titration apparatus according to the dibutylamine method of JIS K-1556.

[0329] In addition, in the above reaction, a known solvent such as methyl ethyl ketone can also be added in an appropriate proportion.

[0330] Next, a cationic active hydrogen compound is incorporated into 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 mixed into the first intermediate reaction product in such a way that the equivalence ratio (isocyanate group / active hydrogen group) of the cationic active hydrogen compound to the active hydrogen group is, for example, 0.95 or more, and also, for example, 1.05 or less.

[0331] The above reaction is carried out under a nitrogen atmosphere. Regarding the reaction conditions, the reaction temperature is, for example, 70°C or higher and 120°C or lower, and the reaction time is 0.5 hours or higher and 4 hours or lower. The reaction is continued until the reaction between the first intermediate product and the cationic active hydrogen compound is complete. Furthermore, a known solvent such as methyl ethyl ketone may be used in the above reaction in an appropriate proportion. Thus, the reaction product of the first intermediate product and the cationic active hydrogen compound (hereinafter referred to as the second intermediate product) is obtained. The second intermediate product has a hydrocarbon group having 12 or more and 30 or fewer carbon atoms and a cationic group.

[0332] Next, an acid compound is incorporated into the second intermediate reaction product. The proportion of the acid compound relative to 1 mole of the cationic active hydrogen compound is, for example, 0.5 moles or more, preferably 3 moles or more, and further, for example, 10 moles or less, preferably 4 moles or less. Thus, the acid compound and the cationic group of the second intermediate reaction product form a salt, yielding a reaction solution containing aliphatic polyisocyanate derivatives, long-chain active hydrogen compounds, cationic active hydrogen compounds, and an acid compound (i.e., carbamate compounds). The above reaction product has a hydrocarbon group with 12 or more and 30 or less carbon atoms and has a cationic group. Furthermore, because the above reaction product has a hydrocarbon group with 12 or more and 30 or less carbon atoms, it can self-disperse (self-emulsify) in water without relying on a dispersant (emulsifier). In other words, the above reaction product can undergo internal emulsification.

[0333] Next, while maintaining the temperature of the reaction solution at, for example, above 50°C and below 100°C, water is added to the reaction solution to emulsify it. Then, the solvent is removed from the reaction solution. This yields an aqueous dispersion containing the above-described reaction product (i.e., a carbamate compound). The solids concentration of the aqueous dispersion is, for example, 10% by mass or more, and, for example, 30% by mass or less.

[0334] These carbamate compounds are reaction products obtained using long-chain active hydrogen compounds, thus exhibiting excellent water repellency, as well as excellent oil repellency, oil resistance, and stain resistance. Furthermore, as reaction products obtained using cationic active hydrogen compounds, they possess enhanced affinity for fibers, resulting in excellent wash durability for the fibers.

[0335] In such carbamate compounds, the concentration of hydrocarbon groups is 30% or more, and preferably 85% or less, and more preferably 50% or less. A hydrocarbon group concentration above the lower limit improves water repellency. Furthermore, a hydrocarbon group concentration below the upper limit improves the stability of the carbamate compound. It should be noted that the hydrocarbon group concentration can be calculated from the amounts of each of the above-mentioned components added.

[0336] It should be noted that, in the above description, firstly, the aliphatic polyisocyanate derivative is reacted with a long-chain active hydrogen compound to obtain a reaction solution containing a first intermediate product. Next, the first intermediate product is reacted with a cationic active hydrogen compound to obtain a reaction solution containing a second intermediate product. Then, the second intermediate product is reacted with an acid compound. However, the order of the reactions is not particularly limited. For example, the aliphatic polyisocyanate derivative can be reacted with the cationic active hydrogen compound first, followed by the reaction with the long-chain active hydrogen compound and the acid compound. 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.

[0337] (Dendromorphic macromolecules)

[0338] Dendritic macromolecular compounds, for example, can be dendritic polymers with a radial structure that branches regularly from the center. To obtain water repellency, dendritic polymers can be compounds with one or more hydrocarbon groups having straight or branched chains at the ends of the branches.

[0339] As a dendritic polymer, for example, the "apolymer extender" disclosed in International Publication No. 2014 / 160906 can be used. For example, a compound obtained by reacting at least one of a compound containing an isocyanate group selected from isocyanates, diisocyanates, polyisocyanates or mixtures thereof with at least one of an isocyanate reactive compound selected from formulas (Ia), (Ib) or (Ic) below can be used.

[0340]

[0341] In the above formula, R 50 Each can be represented independently as -H, R 51 -C(O)R 51 -(CH2CH2O) n (CH(CH3)CH2O) m R 52 、or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R51 Each of n and m independently ranges from 0 to 20, and m+n exceeds 0. Additionally, R... 51 Each is independently an alkyl group with 5 to 29 carbon atoms, either straight or branched, containing one or more unsaturated bonds; R 52 Each is independently -H, or optionally an alkyl group with a straight or branched chain containing one or more unsaturated bonds and having 6 to 30 carbon atoms.

[0342] It should be noted that in equation (Ia), R 50 Or R 52 At least one of them is -H.

[0343] In the above formula, R 53 Each can be represented independently as -H or -R. 51 -C(O)R 51 -,-(CH2CH2O(CH(CH3)CH2O) m R 52 、or -(CH2CH2O(CH(CH3)CH2OC(O)R) 51 R 54 Each can be independently represented by -H, or optionally by a straight or branched alkyl group containing one or more unsaturated bonds with 6 to 30 carbon atoms, or -(CH2CH2O). n’ (CH(CH3)CH2O) m’ R 52 、or -(CH2CH2O(CH(CH3)CH2OC(O)R) 51 Each of n' and m' is independently between 0 and 20, and m+n exceeds 0.

[0344] It should be noted that in equation (Ib), R 52 R 53 Or R 54 At least one of them is -H.

[0345] In the above formula, R 55 -H, -C(O)R 51 、or -CH2C[CH2OR 50 ]3.

[0346] It should be noted that in equation (Ic), R 55 Or R 50 At least one of them is -H.

[0347] There are no particular limitations on the compounds containing isocyanate groups; examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their dimers, trimers, and other modified polyisocyanates. Commercially available products such as "DESMODURN-100" (manufactured by Bayer Corporation, trade name), "Deylanet THA-100" (manufactured by Asahi Kasei Corporation, trade name), and "Deylanet 24A-100" (manufactured by Asahi Kasei Corporation, trade name) can be used. Furthermore, the reaction can be carried out at 80°C for at least one hour.

[0348] 2.1.2 Other components

[0349] The non-fluorinated water-repellent components disclosed herein include specified water-repellent components and may also include components suitable for adhesion treatment to various articles. These may include solvents (dispersion media) and various additives. Furthermore, these solvents and additives may not remain on the surface of the various water-repellent articles after water-repellent treatment. The aqueous medium may be water or a mixture of water and an organic solvent. The amount of organic solvent relative to the aqueous medium may be, for example, 0% by mass or more and 30% by mass or 0% by mass or more and 10% by mass or less. The aqueous medium may consist of only water. Additionally, the treatment solution may contain acids, alkalis, surfactants, chelating agents, etc. Furthermore, the treatment solution may contain other water-repellent additives, other water-repellent components, crosslinking agents, antibacterial and deodorizing agents, flame retardants, antistatic agents, softeners, antifungal agents, etc. In particular, when the treatment solution contains a crosslinking agent, durable water repellency is easily improved. Crosslinking agents will be described later.

[0350] 2.1.3 Content of non-fluorinated water-repellent components

[0351] There are no particular restrictions on the content of non-fluorinated water-repellent components in water-repellent agents. For example, the proportion (mass ratio) of non-fluorinated water-repellent components in the total water-repellent agent can be 0.1% to 70% by mass, or 0.5% to 50% by mass.

[0352] 2.2 Contact Method

[0353] In one embodiment of the method for manufacturing a water-repellent fiber article, the non-fluorinated water-repellent component (a water-repellent treatment agent containing the non-fluorinated water-repellent component) is brought into contact with the pretreated fiber material, thereby allowing the non-fluorinated water-repellent component to adhere to the fiber material. The method for bringing the non-fluorinated water-repellent component (a water-repellent treatment agent containing the non-fluorinated water-repellent component) into contact with the fiber material can be the same as the method for contacting the pretreatment agent described in 1.3.

[0354] 2.3 Heat Treatment

[0355] The preferred fiber material is thoroughly dried before contact with the water-repellent component. The preferred temperature for the dry heat treatment is 100-200°C, particularly 120-180°C. The preferred time for the dry heat treatment is 10 seconds to 3 minutes, particularly 1-2 minutes. There are no particular limitations on the method of dry heat treatment; however, a tenter frame is preferred when the material being treated is in the form of fabric.

[0356] 2.4 Adhesion Amount

[0357] A non-fluorinated water-repellent component is attached to the water-repellent treated fiber material. The treatment using the water-repellent agent is preferably carried out in an amount where the amount of the non-fluorinated water-repellent component relative to 100 parts by weight of the fiber material is 0.1 to 10 parts by weight, or 0.5 to 5 parts by weight. Within this range, a high level of both durable water repellency and a pleasant hand feel can be achieved.

[0358] 3. Combined use of crosslinking agents

[0359] Especially when it is desirable to improve durable water repellency, one embodiment of the method for manufacturing a water-repellent fiber product preferably includes, in addition to pretreating and water-repellent treating the fiber material, attaching a crosslinking agent containing hydroxymethyl melamine, a compound having two or more isocyanate groups, or a terminal isocyanate group to the fiber material and then heating it. Furthermore, when it is desirable to further improve durable water repellency, the pretreatment agent or water-repellent agent preferably comprises a non-fluorinated polymer formed by copolymerizing monomers having functional groups capable of reacting with the aforementioned crosslinking agent. As described above, the compound having two or more isocyanate groups is used. A single crosslinking agent or a combination of multiple agents can be used.

[0360] Crosslinking agents can be applied to the workpiece (fiber product) by immersing it in a treatment solution formed by dissolving the crosslinking agent in an organic solvent or emulsifying and dispersing it in water, and then drying the treatment solution adhering to the workpiece. Furthermore, heating the crosslinking agent adhering to the workpiece allows it to react with the workpiece and the non-fluorinated water-repellent component. To ensure a thorough reaction of the crosslinking agent and more effectively improve durable water repellency, the heating can be performed at 110-180°C for 1-5 minutes. The steps of applying the crosslinking agent and heating can be performed simultaneously with the treatment step using the aforementioned water-repellent agent. When performed simultaneously, for example, the treatment solution containing the non-fluorinated water-repellent component and the crosslinking agent is applied to the workpiece, the water is removed, and then the crosslinking agent adhering to the workpiece is heated. Considering the simplification of the water-repellent processing steps, heat reduction, and economy, it is preferable to perform the treatment simultaneously with the water-repellent agent treatment step.

[0361] In addition, excessive use of crosslinking agents may impair the hand feel. The crosslinking agent is preferably used in an amount of 0.01 to 50 parts by weight, or 0.1 to 10 parts by weight, relative to 100 parts by weight of the treated material (fiber product).

[0362] 4. Uses

[0363] Water-repellent fiber products manufactured through the aforementioned pretreatment and water-repellent treatment exhibit excellent water repellency (initial water repellency and durable water repellency). Furthermore, since these water-repellent fiber products do not use fluorine compounds, they can be considered environmentally friendly. Due to their excellent water repellency, these water-repellent fiber products are suitable for various applications, including down fabrics, outerwear, jackets, windbreakers, smocks, dress shirts, skirts, casual trousers, gloves, hats, bedding fabrics, sun-drying covers, curtains, tents, and other clothing and non-clothing items.

[0364] Example

[0365] As described above, one embodiment of the technology disclosed herein has been illustrated. However, the technology disclosed herein can be modified in various ways beyond the described embodiment without departing from its spirit. Hereinafter, embodiments are shown to describe the technology disclosed herein in more detail, but the technology disclosed herein is not limited to the following embodiments.

[0366] 1. Preparation of pretreatment agents

[0367] The following polyester copolymers (polymer P) with anionic groups were synthesized (synthetic examples A-1 to A-9, comparative synthetic examples A-1 to A-7). 25.0 parts by mass of the polyester copolymers obtained in the synthetic examples and comparative synthetic examples and 75.0 parts by mass of water were added to a reaction vessel and mixed uniformly at 80-90°C to obtain a dispersion (pretreatment agent) containing 25% by mass of the polyester copolymer (preparation examples A-1 to A-9, comparative preparation examples A-1 to A-7).

[0368] 1.1 Synthesis Example A-1

[0369] 155.4 g (0.8 mol) of dimethyl terephthalate, 59.2 g (0.2 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The mixture was stirred under a nitrogen atmosphere, and the temperature was gradually increased from 150 °C to 230 °C over approximately 3 hours to initiate a transesterification reaction, allowing the volatiles to distill off the system. Next, 0.1 g of tetrabutyl titanate was added, and the pressure was slowly reduced to approximately 10 kPa. The reaction was carried out at 250 °C for 2 hours, yielding approximately 224 g of a polyester copolymer. The obtained polyester copolymer contained approximately 72% by mass of dicarboxylic acid units, with a weight-average molecular weight of 19,000.

[0370] 1.2 Synthesis Example A-2

[0371] 165.1 g (0.85 mol) of dimethyl terephthalate, 44.4 g (0.15 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 219 g of a polyester copolymer. The obtained polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 6,500.

[0372] 1.3 Synthesis Example A-3

[0373] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 31 g of ethylene glycol, 52 g of neopentyl glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 235 g of a polyester copolymer. The obtained polyester copolymer contained approximately 65% ​​by mass of dicarboxylic acid units and had a weight-average molecular weight of 65,000.

[0374] 1.4 Synthesis Example A-4

[0375] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 106 g of diethylene glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 244 g of a polyester copolymer. The obtained polyester copolymer contained approximately 62% by mass of dicarboxylic acid units and had a weight-average molecular weight of 9,000.

[0376] 1.5 Synthesis Example A-5

[0377] 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 sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 214 g of a polyester copolymer. The obtained polyester copolymer contained approximately 70% by mass of dicarboxylic acid units and had a weight-average molecular weight of 16,000.

[0378] 1.6 Synthesis Example A-6

[0379] 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 sodium dimethyl 5-sulfoisophthalate, 49.6 g of ethylene glycol, 20.8 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 206 g of a polyester copolymer. The obtained polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 22,000.

[0380] 1.7 Synthesis Example A-7

[0381] 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 dodecanoic 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 added to a reaction vessel. The reaction was carried out in the same manner as in Preparation Example 1, yielding approximately 228 g of a polyester copolymer. The obtained polyester copolymer contained approximately 68% by mass of dicarboxylic acid units and had a weight-average molecular weight of 2,800.

[0382] 1.8 Synthesis Example A-8

[0383] 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 added to a reaction vessel. The reaction was carried out in the same manner as in Preparation Example 1, yielding approximately 213 g of a polyester copolymer. The obtained polyester copolymer contained approximately 69% by mass of dicarboxylic acid units and had a weight-average molecular weight of 4,100.

[0384] 1.9 Synthesis Example A-9

[0385] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 49.6 g of ethylene glycol, 120 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. Otherwise, the reaction was carried out in the same manner as in Preparation Example 1 to obtain approximately 310 g of polyester copolymer. The content of dicarboxylic acid unit in the obtained polyester copolymer was approximately 51% by mass, and the weight average molecular weight was 10,000.

[0386] 1.10 Comparative Synthesis Example A-1

[0387] 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 24 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 256 g of a polyester copolymer. The obtained polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 29,000.

[0388] 1.11 Comparative Synthesis Example A-2

[0389] 126.2 g (0.65 mol) of dimethyl terephthalate, 103.6 g (0.35 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 120 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 347 g of a polyester copolymer. The obtained polyester copolymer contained approximately 53% by mass of dicarboxylic acid units and had a weight-average molecular weight of 41,000.

[0390] 1.12 Comparative Synthesis Example A-3

[0391] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 310 g of polyethylene glycol with a molecular weight of 3100, and 0.1 g of zinc acetate were added to a reaction vessel. Otherwise, the reaction was carried out in the same manner as in Preparation Example 1 to obtain approximately 512 g of polyester copolymer. The polyester copolymer contained approximately 32% by mass of dicarboxylic acid units and had a weight-average molecular weight of 85,000.

[0392] 1.13 Comparative Synthesis Example A-4

[0393] 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of sodium dimethyl 5-sulfoisophthalate, 57 g of ethylene glycol, 86 g of polyethylene glycol with a molecular weight of 1000, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 314 g of a polyester copolymer. The obtained polyester copolymer contained approximately 59% by mass of dicarboxylic acid units and had a weight-average molecular weight of 31,000.

[0394] 1.14 Comparative Synthesis Example A-5

[0395] 186.2 g (0.96 mol) of dimethyl terephthalate, 11.8 g (0.04 mol) of sodium dimethyl 5-sulfoisophthalate, 31 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, 52 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was then carried out in the same manner as in Preparation Example 1, yielding approximately 229 g of a polyester copolymer. The obtained polyester copolymer contained approximately 64% by mass of dicarboxylic acid units and had a weight-average molecular weight of 19,000.

[0396] 1.15 Comparative Synthesis Example A-6

[0397] 135.8 g (0.7 mol) of dimethyl terephthalate, 88.8 g (0.3 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, and 0.1 g of zinc acetate were added to the reaction vessel. Otherwise, the reaction was carried out in the same manner as in Preparation Example 1 to obtain approximately 223 g of polyester copolymer. The polyester copolymer contained approximately 76% by mass of dicarboxylic acid units and had a weight-average molecular weight of 30,000.

[0398] Table 1 below shows the amount (mol%) of a unit derived from a specific dicarboxylic acid (a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group) in all dicarboxylic acid units, the content ratio of the aforementioned dicarboxylic acid unit in the molecule of the polyester copolymer, and the weight-average molecular weight of the polyester copolymer for each polyester copolymer involved in the above synthetic examples and comparative synthetic examples.

[0399]

[0400] 2. Preparation of water-repellent treatment agent

[0401] As a water-repellent agent, a treatment solution containing the following non-fluorinated water-repellent components is prepared.

[0402] 2.1 Preparation of dispersions of acrylic compounds

[0403] (Preparation Example B-1)

[0404] 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 Pharmaceutical Co., Ltd., polyoxyethylene branched decyl ether, HLB=14.7), 0.2 parts by weight of stearyltrimethylammonium sulfate, 10 parts by weight of tripropylene glycol, and 68.8 parts by weight of water were added to an autoclave and mixed at 45°C to prepare a mixture. The mixture was then subjected to ultrasonic irradiation to emulsify and disperse all monomers. Next, 0.2 parts by weight of azobis(isobutylamidine) dihydrochloride was added to the dispersion. Under a nitrogen atmosphere, 4.0 parts by weight of vinyl chloride were continuously injected while maintaining the internal pressure of the autoclave at 0.3 MPa, and free radical polymerization was carried out at 60°C for 6 hours to obtain a dispersion containing 20% ​​by weight of acrylic resin.

[0405] (Preparation Examples B-2 and B-3)

[0406] A dispersion containing 20% ​​by mass of acrylic resin was obtained by following the same steps as in Preparation Example B-1, according to the feeding amounts shown in Table 2 below.

[0407]

[0408] 2.2 Preparation of dispersions of organosilicon compounds

[0409] 2.2.1 Alkyl-modified organosilicon dispersion

[0410] (Preparation Example B-4: Octadecyl polydimethylsiloxane dispersion)

[0411] The molar ratio of SiH:SiCH3 is 5:5 (using...) 1 A mixed solution of methylhydroorganosilicon (NMR) measured by ¹H NMR and ethylene glycol monobutyl ether-toluene, with platinum(IV) as a hydrosilylation catalyst, was loaded into a flask such that the platinum concentration was 5 ppm relative to the reactants in the system. The flask was purged with nitrogen, and 1-octadecene, with a 1 molar equivalent relative to the reactive group (Si-H) of the methylhydroorganosilicon, was added dropwise to the mixture in the flask. The reactor was heated to 120°C and the addition reaction was carried out for 6 hours to obtain an alkyl-modified organosilicon represented by the following formula (1), where R 20 R²¹ and R²² are CH3, and R²³ is C. 18 H 37 a is 40, b is 40, a∶b=1∶1, R 30 ~R 35 The addition reaction was confirmed by FT-IR (Fourier Transform Infrared) spectrophotometry on the resulting alkyl-modified organosilicon, specifically by confirming the disappearance of the absorption spectrum of the SiH group derived from the methylhydrogen organosilicon.

[0412]

[0413] The obtained alkyl-modified organosilicon (20 parts by weight), SPAN40 (a nonionic surfactant of sorbitol, HLB=6.7) (1.2 parts by weight), TWEEN (registered trademark) 40 (a nonionic surfactant of sorbitol, HLB=15.6) (1.3 parts by weight), Noigen XL-40 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5) (0.5 parts by weight), Noigen XL-60 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5) (0.5 parts by weight), stearyltrimethylammonium sulfate (0.5 parts by weight), and dipropylene glycol (10 parts by weight) were mixed while heating. Next, 66.0 parts by mass of water were added little by little to the resulting mixture while mixing, thereby obtaining a dispersion containing 20% ​​by mass of octadecyl polydimethylsiloxane (average HLB of nonionic surfactant = 11.4).

[0414] (Preparation Example B-5: Hexadecyl polydimethylsiloxane dispersion)

[0415] The molar ratio of SiH:SiCH3 is 4:6 (using...) 1 A mixed solution of methylhydroorganosilicon (NMR) measured by ¹H NMR and ethylene glycol monobutyl ether-toluene, with platinum (IV) as a hydrosilylation catalyst, was loaded into a flask such that the platinum concentration was 5 ppm relative to the reactants in the system. The flask was purged with nitrogen, and 1-hexadecene, with a 1 molar equivalent relative to the methylhydroorganosilicon reactive group (Si-H), was added dropwise to the mixture in the flask. The reactor was heated to 120°C and the addition reaction was carried out for 6 hours to obtain the alkyl-modified organosilicon represented by the above formula (1), where R 20 R²¹ and R²² are CH3, and R²³ is C. 26 H 53 a is 60, b is 90, a∶b=2∶3, R 30 ~R 35 The addition reaction was confirmed by FT-IR (Fourier Transform Infrared) spectrophotometry on the resulting alkyl-modified organosilicon, specifically by confirming the disappearance of the absorption spectrum of the SiH group derived from the methylhydrogen organosilicon.

[0416] Using the obtained alkyl-modified organosilicon, a dispersion containing 20% ​​by mass of hexadecyl polydimethylsiloxane (average HLB of nonionic surfactant = 9.8) was obtained in the same manner as in Preparation Example B-4.

[0417] (Preparation Example B-6: Tridodecyl polydimethylsiloxane dispersion)

[0418] The molar ratio of SiH:SiCH3 is 3:7 (using...) 1 A mixed solution of methylhydroorganosilicon (NMR) measured by ¹H NMR and ethylene glycol monobutyl ether-toluene, with platinum (IV) as a hydrosilylation catalyst, was loaded into a flask such that the platinum concentration was 5 ppm relative to the reactants in the system. The flask was purged with nitrogen, and 1-thaldenebenzene, with a 1 molar equivalent relative to the reactive group (Si-H) of the methylhydroorganosilicon, was added dropwise to the mixture in the flask. The reactor was heated to 120°C and the addition reaction was carried out for 6 hours to obtain the alkyl-modified organosilicon represented by the above formula (1), where R 20 R²¹ and R²² are CH3, and R²³ is C. 32 H 65 a is 140, b is 60, a∶b=7∶3, R 30 ~R 35 The addition reaction was confirmed by FT-IR (Fourier Transform Infrared) spectrophotometry on the resulting alkyl-modified organosilicon, specifically by confirming the disappearance of the absorption spectrum of the SiH group derived from the methylhydrogen organosilicon.

[0419] Using the obtained alkyl-modified organosilicon, a dispersion containing 20% ​​by mass of tridodecyl polydimethylsiloxane (average HLB of nonionic surfactant = 8.1) was obtained in the same manner as in Preparation Example B-4.

[0420] The composition of the preparation examples B-4 to B-6 and the average HLB of the nonionic surfactants are summarized in Table 3 below.

[0421]

[0422] 2.2.2 Dispersions of organosilicon resin, dimethyl organosilicon, and amino-modified organosilicon (Preparation Example B-7)

[0423] In a 300 mL stainless steel container, 5.8 parts by weight of MQ-1600 (a trimethylsilyl polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) as an organosilicon resin and 13.4 parts by weight of KF-96A-100cs (manufactured by Shin-Etsu Silicone Co., Ltd.) as a dimethyl organosilicon were added, and the mixture was heated and stirred until the organosilicon resin was uniformly dissolved. Then, 0.8 parts by weight of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., a bi-terminated amino-modified organosilicon with a functional group equivalent of 2200) as an amino-modified organosilicon were added to the resulting homogeneous solution to obtain a mixture. Next, 1.6 parts by weight of Noigen XL-40 were added, and 78.4 parts by weight of water were added little by little while mixing. The mixture was ultrasonically treated at 60-70°C for 10 minutes using an ultrasonic emulsifier, and then cooled to room temperature to obtain a dispersion containing 20% ​​by weight of organosilicon compounds (average HLB of nonionic surfactant = 10.5).

[0424] (Preparation Example B-8)

[0425] The mixing ratios were set as shown in Table 4 below, and a dispersion containing 20% ​​by mass of an organosilicon compound (average HLB of nonionic surfactant = 4.7) was obtained in the same manner as in Preparation Example B-7.

[0426] (Preparation Example B-9)

[0427] The mixing ratios were set as shown in Table 4 below, and a dispersion containing 20% ​​by mass of an organosilicon compound (average HLB of nonionic surfactant = 18.3) was obtained in the same manner as in Preparation Example B-7.

[0428] (Preparation Example B-10)

[0429] The mixing ratios were set as shown in Table 4 below, and a dispersion containing 20% ​​by mass of an organosilicon compound (average HLB of nonionic surfactant = 10.5) was obtained in the same manner as in Preparation Example B-7.

[0430] 2.2.3 Dispersion of amino-modified organosilicon

[0431] (Preparation Example B-11)

[0432] WACKER FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicones Co., Ltd., amine equivalent 3700, solids 100%) was used as the amino-modified organosilicon, and the formulation ratio was set as shown in Table 3 below. Otherwise, a dispersion containing 20% ​​by mass of organosilicon compound (average HLB of nonionic surfactant = 12.0) was obtained in the same manner as in Preparation Example B-7.

[0433] 2.2.4 Dispersion of Organosilicon Resin

[0434] (Preparation Example B-12)

[0435] Using IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) as the solvent, and setting the mixing ratio as shown in Table 3 below, a dispersion containing 20% ​​by mass of silicone resin (average HLB of nonionic surfactant = 4.7) was obtained in the same manner as in Preparation Example A-7.

[0436]

[0437] Additionally, regarding nonionic surfactants, they are SPAN65: HLB2.1 (manufactured by Croda), Noigen XL-160: HLB16.3 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), and NIKKOL BC-30: HLB19.5 (manufactured by Nikko Chemical Co., Ltd.). Regarding Noigen XL-40, the above applies.

[0438] 2.3 Preparation of dispersions of wax compounds

[0439] (Preparation Example B-13)

[0440] In a high-pressure reaction vessel, 20 parts by weight of Paraffin Wax-155 (manufactured by Nippon Seika Co., Ltd., melting point 69°C), 78 parts by weight of water, 1.0 part by weight of dehydrated sorbitan monostearate (HLB=4.5), and 1.0 part by weight of polyoxyethylene dehydrated sorbitan monostearate (HLB=14.9) were placed and sealed. Then, while stirring, the temperature was raised to 110-120°C. The vessel was then subjected to high-pressure emulsification for 30 minutes while maintaining high pressure, yielding an emulsion containing 20% ​​by weight of paraffin wax (average HLB=9.7 for nonionic surfactants).

[0441] 2.4 Preparation of dispersions of carbamate compounds

[0442] 2.4.1 Synthesis of polyurethane resin

[0443] (Synthetic Example U-1)

[0444] In a reactor equipped with a thermometer, stirrer, nitrogen inlet pipe, and condenser, under a nitrogen atmosphere, 500 parts by weight of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenet 700), 0.25 parts by weight of 2,6-di-tert-butyl-4-methylphenol (also known as butylated hydroxytoluene, BHT, hindered phenolic antioxidant), and 0.25 parts by weight of tetraphenyldipropylene glycol diphosphite (organophosphite, co-catalyst) were mixed. Then, 10.7 parts by weight of 1,3-butanediol were 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, followed by cooling to 60°C. Finally, 0.2 parts by weight of trimethyl-N-2-hydroxypropylammonium-2-ethylhexanoate, acting as an isocyanurate esterification catalyst, were added, and the reaction was allowed to proceed for 1.5 hours. Then, 0.04 parts by mass of o-toluenesulfonamide were added relative to 100 parts by mass of HDI. The reaction mixture was then distilled through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) until the residual HDI monomer content was below 0.5%, yielding an aliphatic polyisocyanate derivative (an isocyanurate derivative of hexamethylene diisocyanate). The obtained aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functional group number of 3.0.

[0445] 2.4.2 Preparation of polyurethane resin dispersion

[0446] (Preparation Example B-14)

[0447] In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen inlet pipe, 100.08 parts by mass of an aliphatic polyisocyanate derivative (Synthetic Example U-1), a long-chain active hydrogen compound, and 90.03 parts by mass of Calcor 8098 (stearyl alcohol, manufactured by Kao Corporation) were mixed and reacted at 110°C for 4 hours under a nitrogen atmosphere until the concentration of isocyanate groups reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.89 parts by mass of N-methyldiethanolamine, a cationic active hydrogen compound, were added, and the reaction was carried out at 80°C for 1 hour. As a solvent, 50 parts by mass of methyl ethyl ketone were added, and the reaction was carried out at 80°C until the isocyanate groups disappeared as confirmed by infrared absorption spectroscopy. Next, 57.7 parts by mass of methyl ethyl ketone (MEK) were added to the reaction solution, the temperature was raised to 80°C, and the mixture was stirred until the reaction solution was completely dissolved, then cooled to 75°C. Then, 18.93 parts by mass of acetic acid, as an acid compound, was added for neutralization. Next, while maintaining the reaction solution at 75°C, 20 parts by mass of NIKKOL Hexaglyn 1-SV (HLB=9.0, manufactured by Nikko Chemical Co., Ltd.) were added and mixed, and 800 parts by mass of ion-exchanged water heated to 70°C was slowly added to emulsify. Next, MEK was removed by distillation under reduced pressure at a water bath temperature of 60°C using an evaporator. Then, the solids concentration was adjusted to 20% by mass using ion-exchanged water, thereby obtaining a dispersion containing polyurethane resin (average HLB=9.0 for nonionic surfactant, 20% by mass of solids).

[0448] 2.5 Preparation of dispersions of dendritic macromolecular compounds

[0449] (Preparation Example B-15)

[0450] In a four-necked round-bottom flask equipped with a top stirrer, thermocouple, and dendritic tube, 15.3 parts by weight of dehydrated sorbitol tristearate (hydroxyl value = 77.2 mg KOH / g) and 24.7 parts by weight of 4-methyl-2-pentanone (MIBK) were added. The solution was refluxed for 1 hour to remove residual water. After 1 hour, the solution was cooled to 50°C, and 4.0 parts by weight of DESMODUR N-100 were added, followed by the addition of a catalyst. The solution was then heated for more than 1 hour until it reached 80°C, yielding a dendritic polymer solution.

[0451] 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 dendritic polymer solution prepared above was cooled to 60°C, and the heated surfactant solution was slowly added to prepare a turbid emulsion. After homogenization at 41.37 MPa (6000 psi), the solvent was removed by distillation under reduced pressure to obtain a dispersion containing 20% ​​dendritic macromolecular compounds (average HLB of nonionic surfactant = 14.4, solids content 20% by weight).

[0452] 3. Fiber treatment

[0453] Using the aforementioned pretreatment agent, polyester (PET) fabric was subjected to impregnation, pad dyeing, or dyeing, soaking, and washing treatments to obtain pretreatment agent-treated fabric. Subsequently, the pretreatment agent-treated fabric was subjected to water-repellent treatment with a water-repellent agent, and its water-repellent properties were evaluated. Furthermore, a treatment solution was prepared by diluting the water-repellent agent and crosslinking agent with water, wherein the water-repellent agent content was 6% by mass and the NK Asist FU (crosslinking agent, Nichika Chemical Co., Ltd.) content was 1% by mass.

[0454] 3.1 Impregnation treatment (Examples 1-27, Comparative Examples 1-6)

[0455] After preparing a pretreatment solution by diluting the pretreatment agent with water as shown in Table 5 or 6 below, the fabric to be treated is impregnated in the pretreatment solution at a liquor ratio of 1:10 (by weight, the same below) at 80°C for 20 minutes (pretreatment). After pretreatment, the fabric is dried at 130°C for 1 minute to obtain the pretreated fabric. Then, after preparing a water-repellent treatment solution by diluting the water-repellent treatment agent and crosslinking agent with water as shown in Table 5 or 6, the pretreated fabric is pad-dyed with the water-repellent treatment solution (water-repellent treatment). After water-repellent treatment, the fabric is dried at 170°C for 1 minute to obtain a water-repellent fiber product.

[0456] 3.2 Pad-dyeing treatment (Example 28, Comparative Example 7)

[0457] A pretreatment solution was prepared by diluting the pretreatment agent with water to form the composition shown in Table 6 below. The pretreatment solution was then used to perform pad-dyeing treatment (pretreatment) on the treated fabric. After pretreatment, the fabric was dried at 130°C for 1 minute to obtain the pretreatment agent-treated fabric. Then, a water-repellent treatment solution was prepared by diluting the water-repellent treatment agent and crosslinking agent with water to form the composition shown in Table 6. This water-repellent treatment solution was then used to perform pad-dyeing treatment (water-repellent treatment) on the pretreatment agent-treated fabric. After water-repellent treatment, the fabric was dried at 170°C for 1 minute to obtain a water-repellent fiber product.

[0458] 3.3 Dyeing treatment, soaping treatment and washing treatment (Examples 29-37, Comparative Examples 8-13)

[0459] After the following pretreatment (3.3.1~3.3.4), water-repellent treatment (3.3.5) is performed to obtain water-repellent fiber products.

[0460] 3.3.1 First Method (2-Bath 2-Stage Method): Example 29, Comparative Examples 8-9

[0461] Polyester fibers are dyed and soaped using a 2-bath, 2-stage process.

[0462] 3.3.1.1 Staining treatment

[0463] Using 100% polyester fabric as the test fabric, and a Minicolor dyeing machine (Rapid) as the test equipment, the test fabric was placed in a dyeing solution with the following composition at a liquor ratio of 1:15 and dyed at 130°C for 60 minutes (increasing the temperature from 60°C at 2°C / min).

[0464] <Composition of the staining solution>

[0465] 80% acetic acid 0.4 g / L

[0466] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0467] Disperse dyes

[0468] Foron Rubine (made by ARCHROMA) 4.5%owf

[0469] 3.3.1.2 Soap washing treatment

[0470] After the above dyeing treatment, the dyeing solution is cooled to approximately 80°C and then discharged. A new soaping solution with the following composition is prepared and soaped at 80°C for 20 minutes at a liquor ratio of 1:15.

[0471] <Composition of soap wash>

[0472] Pretreatment agent 0 or 1 g / L

[0473] Sodium hydroxide 48% 1.0g / L

[0474] Sodium dithionite 1.0 g / L

[0475] 3.3.1.3 Cleaning and other treatments, etc.

[0476] The polyester fibers treated with the above soaping are then washed, dehydrated, and dried to obtain dyed polyester fiber products. The washing solution used in the washing process does not contain any pretreatment agents.

[0477] 3.3.2 Second Method (1 Bath 2 Stage Method): Example 30, Comparative Examples 10-11

[0478] Polyester fibers are dyed in a dyeing solution with dyeing auxiliaries and pretreatment agents. Then, a soaping solution is prepared by adding chemicals to the dyeing bath, and soaping is performed on this solution.

[0479] 3.3.2.1 Staining treatment

[0480] Using 100% polyester fabric as the test fabric, and a Minicolor dyeing machine (Rapid) as the test equipment, the test fabric was placed in a dyeing bath with the following composition at a liquor ratio of 1:15 and dyed at 130°C for 60 minutes (increasing the temperature from 60°C at 2°C / min).

[0481] Composition of the staining bath

[0482] 80% acetic acid 0.4 g / L

[0483] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0484] Pretreatment agent 0 or 1 g / L

[0485] Disperse dyes

[0486] Foron Rubine (made by ARCHROMA) 4.5%owf

[0487] 3.3.2.2 Soap washing treatment

[0488] After the above dyeing treatment, the dyeing solution is cooled to approximately 80°C. A soaping solution is prepared by adding the following agents, and then soaping is performed at 80°C for 20 minutes. Here, the ratio of polyester fibers to the soaping solution is maintained at 1:15, and the following agents are added at a concentration of 1 g / L.

[0489] <Pharmaceuticals>

[0490] 48% caustic soda 1g / L

[0491] Sodium dithionite 1g / L

[0492] 3.3.2.3 Cleaning and other treatments, etc.

[0493] The polyester fibers treated with the above soaping are then washed, dehydrated, and dried to obtain dyed polyester fiber products. The washing solution used in the washing process does not contain any pretreatment agents.

[0494] 3.3.3 Third Method (1 Bath 2 Stage Method): Examples 31-34, Comparative Examples 12-13

[0495] Polyester fibers are dyed using dyeing auxiliaries in a dyeing bath. Then, a soaping solution is prepared by adding pretreatment agents and chemicals to the dyeing bath, and soaping is performed on this solution.

[0496] 3.3.3.1 Staining treatment

[0497] Using 100% polyester fabric as the test fabric, and a Minicolor dyeing machine (Rapid) as the test equipment, the test fabric was placed in a dyeing solution with the following composition at a liquor ratio of 1:15 and dyed at 130°C for 60 minutes (increasing the temperature from 60°C at 2°C / min).

[0498] <Composition of the staining solution>

[0499] 80% acetic acid 0.4 g / L

[0500] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0501] Disperse dyes

[0502] Foron Rubine (made by ARCHROMA) 4.5%owf

[0503] 3.3.3.2 Soap washing treatment

[0504] After the above dyeing treatment, the dyeing solution is cooled to approximately 80°C. A soaping solution is prepared by adding the following agents, and then soaping is performed at 80°C for 20 minutes. Here, the ratio of polyester fibers to the soaping solution is maintained at 1:15, and the following agents are added in the amounts described below.

[0505] <Pharmaceuticals>

[0506] Pretreatment agent 1g / L

[0507] 48% caustic soda or 1g / L or 5g / L soda ash

[0508] Sodium dithionite or thiourea dioxide 1g / L

[0509] 3.3.3.3 Cleaning treatment

[0510] The polyester fibers treated with the above soaping are then washed, dehydrated, and dried to obtain dyed polyester fiber products. The washing solution used in the washing process does not contain any pretreatment agents.

[0511] 3.3.4 Others (1-bath 2-stage method): Examples 35-37

[0512] The above describes the case where only one specified pretreatment agent is added to the dyeing solution or soaping solution. The following describes the case where a pretreatment agent is added to the cleaning solution used in the soaping solution and the subsequent cleaning process (hot water washing and / or water washing), and the case where a pretreatment agent is added to the cleaning solution used in the subsequent cleaning process (hot water washing and / or water washing).

[0513] 3.3.4.1. Dyeing and soaping treatment

[0514] After dyeing in the same manner as in the third method described above, the dyeing solution is cooled to approximately 80°C. A soaping solution is prepared by optionally adding the following agents, and then soaping is performed at 80°C for 20 minutes. Here, the ratio of polyester fibers to the soaping solution is maintained at 1:15, and the following agents are added in the amounts described below.

[0515] Pretreatment agent 0 or 0.5 g / L

[0516] 48% caustic soda 1g / L

[0517] Sodium dithionite 1g / L

[0518] 3.3.4.2 Cleaning Treatment

[0519] After the above soaping treatment, a cleaning solution is prepared by adding the following agents. Based on this, a hot water washing treatment is performed at 80°C for 20 minutes, or a water washing treatment is performed at 30°C for 20 minutes. Here, the bath ratio of polyester fibers to the cleaning solution is 1:15, and the amount of the following agents is adjusted as described below. Then, dehydration and drying are performed to obtain polyester dyed fiber products.

[0520] <Pharmaceuticals>

[0521] Pretreatment agent 0.5 g / L or 1 g / L

[0522] 3.3.5 Water-repellent treatment

[0523] After the above pretreatment (3.3.1~3.3.4), the water-repellent agent and crosslinking agent are diluted with water to prepare a treatment solution in the manner shown in Table 7. Based on this treatment solution, the pretreated fabric is subjected to pad-dyeing treatment (water-repellent treatment). After water-repellent treatment, the fabric is dried at 170°C for 1 minute to obtain a water-repellent fiber product.

[0524] 4. Evaluation Methods

[0525] 4.1 Evaluation of initial water repellency

[0526] The water repellency of the above-mentioned water-repellent fiber products was evaluated by spraying according to the spraying method of JIS L1092 (2009) with the spray water temperature set at 20°C. The evaluation results were visually assessed according to the following grades. It should be noted that a "+" is marked for slightly better properties, and a "-" is marked for slightly worse properties.

[0527] Water repellency: status

[0528] 5: No moisture adhered to the surface.

[0529] 4: The surface shows slight signs of moisture.

[0530] 3: The surface shows signs of partial dampness.

[0531] 2: The surface appears moist.

[0532] 1: The surface appears generally moist.

[0533] 0: Both the inside and outside of the surface show complete moisture.

[0534] 4.2 Evaluation of durable water repellency

[0535] The above-mentioned water-repellent fiber products were washed 20 times (L-20) according to method 103 of JIS L0217 (1995), and the water repellency after air drying was evaluated according to the same steps and grades as above.

[0536] 4.3 Evaluation of Friction Fastness

[0537] For the aforementioned water-repellent fiber products, dry rubbing fastness and wet rubbing fastness were evaluated. Dry rubbing fastness and wet rubbing fastness were determined according to the Type II (vibration type) method of the friction testing machine as described in JIS L0849:2013, and the fastness was determined using the staining grey scale (JIS L0805:2005). A higher evaluation grade indicates better fastness. Furthermore, each grade was subdivided into four levels to represent subtle differences in fastness. For example, grades 4 and 5 were represented as 4.3, 4.5, and 4.8. The same applies to other grades.

[0538] 4.4 Evaluation of Mechanical Stability

[0539] The water-repellent agent (Preparation Example B-3) and the pretreatment agent (Preparation Examples A-1 to A-9, Comparative Preparation Examples A-1 to A-6) were prepared in the manner shown in Table 8 below. The water-repellent agent and the pretreatment agent were diluted with tap water to prepare 500 mL solutions (Examples 38 to 46, Comparative Examples 14 to 19). After stirring the solution in a homogenizer at a speed of 5,000 rpm for 10 minutes, the resulting scum was filtered onto black cotton cloth, and the clumps remaining on the surface of the cotton cloth were visually assessed.

[0540] 5: No aggregates

[0541] 4: Slightly condensed matter

[0542] 3: Overall, the skin has become lighter and whiter.

[0543] 2: Overall, there is a white condensate remaining.

[0544] 1: Cannot filter

[0545] 5. Evaluation Results

[0546] The evaluation results are shown in Tables 5-8 below.

[0547]

[0548] The results shown in Tables 5-8 indicate that: (1) When the fiber material is treated with a polyester copolymer having specified anionic groups and then subjected to water-repellent treatment with a water-repellent agent (Examples 1-37), the initial water repellency, wash-resistant water repellency and rubbing fastness of the water-repellent fiber product are improved compared with Comparative Examples 1-13.

[0549] (2) The effect of the above pretreatment does not depend on the treatment method. In the case of immersion treatment (Examples 1-27), pad dyeing treatment (Example 28), and dyeing treatment, the effect of the pretreatment is not affected by the treatment method. soap washing treatment In one or more of the cleaning processes (Examples 29-37), the same level of effect was obtained.

[0550] (3) The above pretreatment agents can be used to perform water repellency treatment without reducing the stability of the water repellent bath (Examples 38-46, Comparative Examples 14-19).

[0551] Based on the above results, it can be said that a fiber product with excellent water repellency can be manufactured by the following method of manufacturing fiber products, which includes the steps of contacting a polyester copolymer with anionic groups with a fiber material, and contacting the fiber material after contacting the polyester copolymer with anionic groups with a non-fluorinated water-repellent component.

[0552] Furthermore, while the above embodiments illustrate a method of imparting water repellency to fiber articles using polyester copolymers with anionic groups and non-fluorinated water-repellent components, the technology disclosed herein is not limited to this method. It can be considered that the treatment method of this disclosure can also impart excellent initial and durable water repellency to various articles other than fiber materials. In particular, as shown in the above embodiments, it is suitable for imparting durable water repellency to fiber materials.

Claims

1. A method for manufacturing a water-repellent fiber article, comprising contacting a polyester copolymer having anionic groups with a fiber material, and contacting the fiber material after contacting the polyester copolymer having anionic groups with a non-fluorinated water-repellent component. The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises at least 5 mol% and 30 mol% of at least one of the following units: 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; the diol unit is derived from a diol with a molecular weight of 48 or more and 900 or less. The dicarboxylic acid unit in the polyester copolymer contains more than 50% by mass and less than 75% by mass.

2. A method for manufacturing a water-repellent fiber article, comprising contacting a polyester copolymer having anionic groups with polyester fibers, and contacting the polyester fibers after contacting the polyester copolymer having anionic groups with a non-fluorinated water-repellent component. The method of contacting a polyester copolymer having anionic groups comprises: Dyeing process for polyester fibers; The polyester fibers after the dyeing treatment are subjected to a soaping treatment in the same bath or a different bath as the dyeing solution; and The polyester fibers after the soaping treatment are subjected to one or both of the following cleaning treatments: hot water washing and water washing. One or both of the soaping solution used in the soaping treatment and the cleaning solution used in the cleaning treatment contain the polyester copolymer having anionic groups. The polyester copolymer having anionic groups comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises at least 5 mol% and less than 30 mol% of at least one of the following units: units derived from dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group, and units derived from tricarboxylic acids. The diol unit is derived from diols with a molecular weight of 48 or more and 900 or less, and, The dicarboxylic acid unit in the polyester copolymer having anionic groups contains 50% by mass or more and 75% by mass or less in the molecule.

3. The method for manufacturing the water-repellent fiber product according to claim 2, comprising: The polyester fibers after the dyeing treatment are subjected to the soaping treatment in the same bath as the dyeing solution. The dyeing solution used in the dyeing process contains the polyester copolymer having anionic groups, and At least a portion of the polyester copolymer with anionic groups contained in the dyeing solution is used as at least a portion of the polyester copolymer with anionic groups contained in the soaping solution.

4. The method for manufacturing the water-repellent fiber product according to claim 2, comprising: For the polyester fibers with anionic groups after dyeing, a soaping treatment with anionic groups is performed in the same bath as the dyeing solution, and... The soaping solution used in the soaping process is prepared by adding at least the polyester copolymer having anionic groups to the dyeing solution after the dyeing process.

5. The method for manufacturing a water-repellent fiber product according to any one of claims 1 to 4, wherein the non-fluorinated water-repellent component is at least one of acrylic compounds, organosilicon compounds, wax compounds, carbamate compounds, and dendritic macromolecular compounds.

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