Manufacturing methods for textile products

Abstract

To provide a method for producing a fibrous product demonstrating excellent water repellency.SOLUTION: This method for producing a fibrous product includes: bringing an isocyanate compound into contact with a fibrous material; and bringing a non-fluorine-based water-repellent component into contact with the fibrous material that has already been brought into contact with the isocyanate compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application discloses a method for manufacturing textile products. [Background technology]

[0002] Fluorine-based water repellents containing fluorine groups are known. By treating articles such as textile products with a fluorine-based water repellent, excellent water repellency can be imparted to the articles. Fluorine-based water repellents are generally produced by polymerizing or copolymerizing monomers having fluoroalkyl groups. In order to exhibit sufficient water repellency, it is necessary to adjust the orientation of the fluoroalkyl groups, and typically, after applying the fluorine-based water repellent to the article, it is subjected to heat treatment at a temperature exceeding 130°C. However, such heat treatment is undesirable from the standpoint of energy conservation. Furthermore, monomers having fluoroalkyl groups are not only expensive but also difficult to decompose, thus placing a heavy burden on the environment. For these reasons, in recent years, technologies have been investigated to impart excellent water repellency to articles such as textile products by treating them with fluorine-free, non-fluorine-based water repellents. For example, Patent Documents 1 to 3 disclose a technology in which a non-fluorine-based water repellent is brought into contact with fibers pre-treated with an anionic compound. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-210704 [Patent Document 2] Japanese Patent Publication No. 2019-026965 [Patent Document 3] International Publication No. 2015 / 083627 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Conventional technologies using non-fluorine-based water repellents still have room for improvement. For example, the water repellency under harsh conditions such as wash durability in natural fibers or Bundesmann rain tests in synthetic fibers may not be sufficient. In this regard, there is a need for new technologies that can impart excellent water repellency to textile products (for example, wash durability in natural fibers or water repellency after Bundesmann rain tests in synthetic fibers (Bundesmann water repellency)). [Means for solving the problem]

[0005] This application discloses several embodiments as means for solving the above-mentioned problems. <Aspect 1> Contacting the fibrous material with an isocyanate compound, and After contacting the fiber material with the isocyanate compound, a non-fluorine water-repellent component is brought into contact with the fiber material. A method for manufacturing textile products, including <Aspect 2> The isocyanate compound is a polyisocyanate. A method for manufacturing a textile product according to Embodiment 1. <Aspect 3> The isocyanate compound is at least one of aliphatic isocyanates, aromatic isocyanates, aromatic aliphatic isocyanates, and alicyclic isocyanates. A method for manufacturing a textile product according to embodiment 1 or 2. <Aspect 4> The isocyanate compound is a non-blocked isocyanate. A method for manufacturing a textile product according to any of the embodiments 1 to 3. <Aspect 5> The non-fluorinated water-repellent component is at least one of acrylic compounds, silicone compounds, wax compounds, urethane compounds, and dendrimer compounds. A method for manufacturing a textile product according to any of embodiments 1 to 4. [Effects of the Invention]

[0006] According to the manufacturing method of the present disclosure, by contacting a fiber material with an isocyanate compound and then with a non-fluorinated water-repellent component, the adhesion of the non-fluorinated water-repellent component to the fiber material is improved, and excellent water repellency can be imparted to the fiber material. According to the technology of the present disclosure, for example, it is possible to manufacture textile products having excellent initial water repellency, durable water repellency, and Bundesmann water repellency. [Brief explanation of the drawing]

[0007] [Figure 1] This shows the evaluation criteria for the Bundesmann rainfall test. [Modes for carrying out the invention]

[0008] The following describes a method for manufacturing a textile product according to one embodiment, but the method for manufacturing a textile product according to this disclosure is not limited to this embodiment.

[0009] A method for manufacturing a textile product according to one embodiment includes contacting a fiber material with an isocyanate compound, and then contacting the fiber, after contact with the isocyanate compound, with a non-fluorine water-repellent component. In other words, a method for manufacturing a textile product according to one embodiment involves pre-treating the fiber material with an isocyanate compound, followed by a water-repellent treatment with a non-fluorine water-repellent component.

[0010] 1. Pre-treatment In a method for manufacturing a textile product according to one embodiment, an isocyanate compound is brought into contact with the fiber material as a pretreatment.

[0011] 1.1 Textile materials There are no particular restrictions on the type of fiber material. The fiber material may be at least one selected from natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), nonwoven fabrics, and paper. In a water-repellent fiber product according to one embodiment, the fiber material preferably contains polyamide and polyester as materials from the viewpoint of having better water repellency, and in particular, it is preferable that it be at least one selected from nylon such as nylon 6 and nylon 6,6; polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid; and mixed fibers containing these.

[0012] 1.2 Pretreatment Agents In a method for manufacturing a textile product according to one embodiment, an isocyanate compound is brought into contact with the above-mentioned fiber material. For example, a pretreatment agent containing an isocyanate compound is prepared, and the pretreatment agent is brought into contact with the fiber material. The pretreatment agent contains an isocyanate compound and may optionally contain components other than the isocyanate compound (other components).

[0013] 1.2.1 Isocyanate Compounds The isocyanate compound is any compound having an isocyanate group that can adhere to fibers. For example, the isocyanate compound may be a polyisocyanate. Furthermore, the isocyanate compound may be at least one of aliphatic isocyanates, aromatic isocyanates, aromatic aliphatic isocyanates, and alicyclic isocyanates. The isocyanate compound may be a blocked isocyanate or an unblocked isocyanate. In particular, a superior water-repellent effect can be expected when the isocyanate compound is an unblocked isocyanate. The isocyanate compound can be used alone or in combination of two or more types. Furthermore, the isocyanate compound may be a reaction product of two or more isocyanate compounds.

[0014] (Polyisocyanate) The isocyanate compound may also be a polyisocyanate. Examples of polyisocyanates include polyisocyanate monomers and polyisocyanate derivatives. A polyisocyanate is an isocyanate compound having multiple isocyanate groups in its molecule. Similarly, a diisocyanate compound is an isocyanate compound having two isocyanate groups in its molecule. These polyisocyanates can be used individually or in combination of two or more types.

[0015] There are no particular limitations on the polyisocyanate monomers, and examples include aliphatic polyisocyanates, aromatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers can be used individually or in combination of two or more types.

[0016] There are no particular limitations on the polyisocyanate derivatives, and examples include polymers of polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate modified, iminooxadiazinedione modified), pentamers, heptamers, etc.), allophanate modified forms (e.g., allophanate modified forms produced by adding isocyanate groups of polyisocyanate monomers to urethane groups formed by the reaction of the above-mentioned polyisocyanate monomer with a low molecular weight polyol described later), adduct forms (e.g., adduct forms (alcohol adducts) produced by the reaction of polyisocyanate monomer with a low molecular weight polyol described later), biuret modified forms (e.g., Examples of polyisocyanate derivatives include biuret derivatives (e.g., those produced by the reaction of the polyisocyanate monomer with water or amines), urea derivatives (e.g., those produced by the addition of an isocyanate group of the polyisocyanate monomer to a urea group formed by the reaction of the polyisocyanate monomer with a diamine), oxadiazinetrione derivatives (e.g., oxadiazinetriones produced by the reaction of the polyisocyanate monomer with carbon dioxide), carbodiimide derivatives (e.g., carbodiimide derivatives produced by the decarboxylation condensation reaction of the polyisocyanate monomer), uretdione derivatives, and uretonimine derivatives. Furthermore, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) can also be used as polyisocyanate derivatives. These polyisocyanate derivatives can be used individually or in combination of two or more types.

[0017] From the viewpoint of Bundesmann water repellency, polyisocyanates are preferably polymers of the monomers described above. In particular, Bundesmann water repellency is more easily improved when the polyisocyanate is a trimer.

[0018] As described above, polyisocyanates may be used individually or in combination of two or more. Alternatively, the polyisocyanate may be a reaction product of two or more isocyanate compounds. When two or more polyisocyanates are used in combination, a combination of aliphatic and alicyclic polyisocyanates is preferred. In this case, the mass ratio of aliphatic polyisocyanate to alicyclic polyisocyanate is preferably 99 / 1 to 1 / 99, more preferably 90 / 10 to 10 / 90, even more preferably 80 / 20 to 20 / 80, and most preferably 75 / 25 to 50 / 50. When aliphatic and alicyclic polyisocyanates are included in this ratio, the durable water repellency of Bundesmann is further improved.

[0019] (Aliphatic isocyanates) The aliphatic isocyanate may be at least one selected from, for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, lysine diisocyanate, dimer acid diisocyanate, etc. From the viewpoint of excellent wash-durability water repellency in natural fibers, 1,6-hexamethylene diisocyanate (HDI) is preferred as the aliphatic isocyanate.

[0020] (Aromatic isocyanates) The aromatic isocyanate may be at least one selected from, for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, etc.

[0021] (Aromatic aliphatic isocyanates) The aromatic aliphatic isocyanate may be at least one selected from, for example, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramethyl xylylene diisocyanate or a mixture thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

[0022] (Alicyclic isocyanates) Alicyclic isocyanates include, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate), these Trans,Trans- The alicyclic isocyanate may be at least one selected from the following: (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI, hydrogenated XDI), (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof). From the viewpoint of excellent Bundesmann-durable water repellency, the alicyclic isocyanate is preferably at least one of isophorone diisocyanate (IPDI), hydrogenated MDI, and hydrogenated XDI, more preferably at least one of isophorone diisocyanate (IPDI) and hydrogenated MDI, and even more preferably isophorone diisocyanate (IPDI).

[0023] (Blocked isocyanates / unblocked isocyanates) The isocyanate compound may or may not be blocked by a blocking agent. In particular, from the viewpoint of durable water repellency, an unblocked isocyanate compound (unblocked isocyanate) is preferred. Blocked isocyanates can be obtained by reacting the above-mentioned isocyanate compound with a blocking agent. The blocking agent may be used alone or in combination of two or more types.

[0024] The blocking agent may be, for example, a compound having one or more active hydrogen atoms in its molecule. The blocking agent may be at least one selected from, for example, alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds, imine compounds, pyrazole compounds, and bisulfites. In particular, at least one selected from acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds is preferred. For example, at least one selected from ε-caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole is preferred, and among these, from the viewpoint of wash-resistant water repellency, one or both of dimethylpyrazole and diester malonate are more preferred.

[0025] (self-emulsifying) The above-mentioned isocyanate compounds may or may not have self-emulsifying properties. Examples of isocyanate compounds with self-emulsifying properties include those in which a nonionic hydrophilic group, a cationic hydrophilic group, or anionic hydrophilic group is introduced into a portion of the polyisocyanate. From the viewpoint of water repellency, a polyisocyanate into which a nonionic hydrophilic group having an oxyethylene group is introduced can preferably be used. Examples of hydrophilic compounds reacted with polyisocyanates to impart self-emulsifying properties include polyoxyalkylene monoalkyl ethers such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol polypropylene glycol monomethyl ether, and polypropylene glycol polyethylene glycol monobutyl ether; ethylene glycol, or (poly)ethylene glycols such as diethylene glycol, triethylene glycol, and polyethylene glycol; block copolymers and random copolymers of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; random copolymers and block copolymers of ethylene oxide and propylene oxide, and ethylene oxide and butylene oxide; polyoxyalkylene monoamines and polyoxyalkylenediamines; and polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether are preferred. The above nonionic hydrophilic compounds may be used individually or in combination of two or more. By introducing these compounds at an amount of about 1 to 50 mol% relative to the isocyanate group, self-emulsifying properties can be imparted to the isocyanate compound.

[0026] 1.2.2 Other Ingredients The pretreatment agent may, for example, contain other components such as solvents and emulsifiers in addition to the isocyanate compound mentioned above.

[0027] (solvent) The pretreatment agent may contain, for example, water, an organic solvent, or a mixture of water and an organic solvent. Examples of organic solvents include ether-based solvents, ketone-based solvents, hydrocarbon-based solvents, aromatic-based solvents, ester-based solvents, and nitrogen-containing solvents. The amount of solvent may be 0.1 to 70% by mass, 5 to 50% by mass, or 10 to 30% by mass, based on 100% by mass of the total pretreatment agent.

[0028] (emulsifier) The pretreatment agent may contain an emulsifier to improve the dispersibility of isocyanate compounds and the like in the solvent. The emulsifier may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In the case of blocked isocyanates, from the viewpoint of water repellency, the emulsifier is preferably a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant. In the combination of a nonionic surfactant and a cationic surfactant, the mass ratio of the nonionic surfactant to the cationic surfactant may be, for example, 99.5:0.5 to 50:50, or 99:1 to 90:10. In the case of unblocked isocyanates, from the viewpoint of protecting the isocyanate group, an anionic surfactant is most preferred.

[0029] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkyl alkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol, polypropylene glycol block copolymers, and the like. Examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, vinyl sulfosuccinates, polyoxyalkylene alkyl ether phosphates, and polyoxyalkylene alkylphenyl ether phosphates. Examples of cationic surfactants include amine salts, amideamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples, though not limited to them, include amine salt-type surfactants such as alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride. Amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, and acetate betaines, specifically long-chain amine oxides, lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.The amount of these surfactants used is not particularly limited, but for example, it is preferably 1 to 20% by mass of the solid content of the emulsion, and more preferably 1.5 to 10% by mass.

[0030] The hydrophilic-lipophilic balance (HLB) of the emulsifier described above is not particularly limited. In one embodiment of the pretreatment agent, the average HLB of the nonionic emulsifier is preferably 6.0 to 16.0, 6.5 to 15.5, 7.0 to 15.0, or 7.5 to 14.5. If the HLB falls outside this range, the initial and post-wear Bundesmann water repellency tends to decrease. The HLB of the emulsifier is determined by considering the ethylene oxy groups in the surfactant as hydrophilic groups and using the following formula by the Griffin method. HLB = 20 × [(Molecular weight of hydrophilic group contained in surfactant) / (Molecular weight of surfactant)]

[0031] (Other additives) The pretreatment agent may contain acids, alkalis, chelating agents, etc.

[0032] 1.2.3 Content of isocyanate compounds The content of isocyanate compounds in the pretreatment agent is not particularly limited. For example, the ratio (mass percentage) of isocyanate compounds to the total pretreatment agent may be 0.01 to 80%, or 0.1 to 70%.

[0033] 1.3 Contact method In a method for manufacturing a textile product according to one embodiment, the isocyanate compound (pretreatment agent containing the isocyanate compound) can be brought into contact with the above-mentioned textile material to adhere the isocyanate compound to the textile material. The method for bringing the above-mentioned isocyanate compound (pretreatment agent containing the isocyanate compound) into contact with the above-mentioned textile material is not particularly limited. For example, processing methods such as immersion, spraying, and coating can be used. The immersion method may be a continuous method or a batch method. In the continuous method, first, the isocyanate compound is diluted in a solvent to prepare a pretreatment agent (treatment solution). Next, the workpiece (textile material) is continuously fed into an impregnation device filled with the treatment solution, and after impregnating the workpiece with the treatment solution, the excess treatment solution is removed. The impregnation device is not particularly limited, and padders, squirrel-type impregnation devices, gravure coater-type impregnation devices, spray-type impregnation devices, foam-type impregnation devices, coating-type impregnation devices, etc., can be preferably used, with padder type being particularly preferred. Subsequently, an operation is performed to remove the solvent remaining on the workpiece using a dryer. The dryer is not particularly limited, but a spread dryer such as a hot flooler or tenter is preferred. The continuous method is preferably used when the material to be treated is a fabric such as a woven cloth. On the other hand, the batch method consists of, for example, a step of immersing the material to be treated in a treatment solution and a step of removing the solvent remaining on the treated material. The batch method is preferably used when the material to be treated is not a fabric, for example, loose hair, top, sliver, hank, tow, yarn, etc., or when the continuous method is unsuitable, such as for knitted fabrics. In the immersion step, for example, a cotton dyeing machine, cheese dyeing machine, liquid flow dyeing machine, industrial washing machine, beam dyeing machine, etc. can be used. In the solvent removal operation, a cheese dryer, beam dryer, hot air dryer such as a tumble dryer, high-frequency dryer, etc. can be used.

[0034] 1.4 Drying It is preferable to thoroughly dry the fibrous material after contacting it with a pretreatment agent (treatment solution). The temperature for the dry heat treatment is preferably 100 to 200°C, and particularly preferably 120 to 180°C. The duration of the dry heat treatment is preferably 10 seconds to 3 minutes, and particularly preferably 1 to 2 minutes. There are no particular limitations on the method of dry heat treatment, but a tenter is preferred when the material to be treated is in the form of a fabric.

[0035] 1.5 Amount of adhesion The fiber material will have an isocyanate compound attached to it after pretreatment. It is preferable to treat the fiber material with the pretreatment agent in an amount such that the amount of isocyanate compound attached is 0.01 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0036] 2. Water-repellent treatment In a method for manufacturing a textile product according to one embodiment, a non-fluorinated water-repellent component is brought into contact with the fiber material after the above-mentioned pretreatment (after contact with the isocyanate compound). 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.

[0037] 2.1 Water-repellent treatment agents The water-repellent treatment agent contains a non-fluorine-based water-repellent component and may optionally contain components other than the non-fluorine-based water-repellent component (other components).

[0038] 2.1.1 Non-fluorine-based water-repellent components The non-fluorinated water-repellent component may be, for example, at least one of acrylic compounds, silicone compounds, wax compounds, and dendrimer compounds. From the viewpoint of durable water repellency and Bundesmann water repellency, one or both of acrylic compounds and silicone compounds are preferred as the non-fluorinated water-repellent component, and silicone compounds are more preferred.

[0039] (Acrylic compounds) Acrylic compounds have constituent units derived from, for example, a (meth)acrylic acid ester monomer represented by the following general formula (A1) (hereinafter also referred to as "component (A1)"). Acrylic compounds may further have constituent units derived from a compound represented by the following general formula (A2) (hereinafter also referred to as "component (A2)"). In this application, "(meth)acrylic acid ester" means "acrylic acid ester" or the corresponding "methacrylic acid ester," and the same applies to "(meth)acrylic acid," "(meth)acrylamide," etc.

[0040] [ka] [In formula (A1), R 1 R is a hydrogen or methyl group, 2 This is a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have substituents.

[0041] [ka] [In formula (A2), R 11 R is a hydrogen or methyl group, 12 is a divalent hydrocarbon group having 1 to 6 carbon atoms, Z is an ester group or amide group, and W is -CO-R 13 (R 13 The group is represented by -NH-CO-NH2 (where is a monovalent hydrocarbon group having 1 to 4 carbon atoms), or by the following formula (W1).

[0042] [ka]

[0043] The above component (A1) has 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. Among these, a linear structure is preferred from the viewpoint of water repellency, and a linear alkyl group is more preferred. In this case, water repellency is superior. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has substituents, examples of substituents include one or more from hydroxyl groups, amino groups, carboxyl groups, epoxy groups, isocyanate groups, blocked isocyanate groups, and (meth)acryloyloxy groups. In the above general formula (A-1), R 2 It is preferable that the group is an unsubstituted hydrocarbon group.

[0044] The number of carbon atoms in the hydrocarbon group is preferably 12 to 24, and more preferably 12 to 22. When the number of carbon atoms is within this range, the water repellency and texture become particularly excellent. Particularly preferred as a hydrocarbon group is a linear alkyl group with 18 to 22 carbon atoms.

[0045] Examples of component (A1) above include at least one selected from stearyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, and behenyl (meth)acrylate.

[0046] The above component (A1) may have at least one functional group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups that can react with a crosslinking agent. In this case, durable water repellency can be further improved. The isocyanate group may form a blocked isocyanate group protected by a blocking agent. Furthermore, if the above component (A1) has an amino group, the texture can be further improved.

[0047] The component (A1) is preferably a monofunctional (meth)acrylic acid ester monomer having one polymerizable unsaturated group per molecule.

[0048] The component (A1) may be used alone in one kind, or may be used in combination of two or more kinds.

[0049] In the above formula (A2), R 12 may be linear or branched, may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may further have an alicyclic cyclic structure.

[0050] In the above formula (A2), when Z is an ester group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is preferably a group represented by -NH-CO-NH2 or a group represented by the above formula (W1). When Z is an amide group, R 12 is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is -CO-R 13 is preferably a group represented by, and R 13 preferably has 1 to 2 carbon atoms.

[0051] The component (A2) is not particularly limited, and examples thereof include diacetone acrylamide, 2-(2-oxo-2-imidazolidinyl)ethyl 2-methylprop-2-enoate, and N-[2-(2-oxoimidazolidin-3-yl)ethyl]methacrylamide. Among these, from the viewpoint of durable water repellency, diacetone acrylamide and 2-(2-oxo-2-imidazolidinyl)ethyl 2-methylprop-2-enoate are preferable as the component (A2).

[0052] The component (A2) may be used alone in one kind, or may be used in combination of two or more kinds.

[0053] In acrylic compounds, the ratio of constituent units derived from component (A1) to constituent units derived from component (A2) is preferably such that the ratio (A1) / (A2) of the mass of component (A1) to the mass of component (A2) is 100 / 0 to 70 / 30, more preferably 99.9 / 0.1 to 70 / 30, even more preferably 99.8 / 0.2 to 80 / 20, and particularly preferably 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, the durable water repellency and water-repellent properties are better.

[0054] The total mass of component (A1) and component (A2) to be blended is preferably 60 to 100% by mass, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass, relative to the total amount of monomer components constituting the acrylic compound.

[0055] From the viewpoint of peel strength, it is preferable that the acrylic compound contains, in addition to component (A1) and an optional component (A2), at least one monomer (A3) (hereinafter also referred to as "component (A3)") from vinyl chloride and vinylidene chloride as a monomer component.

[0056] (A3) From the viewpoint of maintaining the texture of the textile product, vinyl chloride is preferred as the component.

[0057] The amount of component (A3) to be added is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, relative to the total mass of components (A1) and (A2) of 100 mass, from the viewpoint of water repellency, durable water repellency, and peel strength. The amount of component (A3) to be added is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less, relative to the total mass of components (A1) and (A2) of 100 mass, from the viewpoint of water repellency, durable water repellency, and texture.

[0058] It is preferable that the acrylic compound contains, in addition to component (A1) and any component (A2), at least one reactive emulsifier (A4) (hereinafter also referred to as "component (A4)") selected from the following: a compound having an HLB of 7 to 18 and represented by the following general formula (A4-1); a compound having an HLB of 7 to 18 and represented by the following general formula (A4-2); and a compound having an HLB of 7 to 18 and obtained by adding a C2-C4 alkylene oxide to an oil or fat having a hydroxyl group and a polymerizable unsaturated group (A4-3), in order to improve the emulsion stability in the composition during emulsion polymerization or dispersion polymerization.

[0059] [ka] [In formula (A4-1), R 3 X is a hydrogen or methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and Y 1 It is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms.

[0060] [ka] [In formula (A4-2), R 4 Y is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. 2 It is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms.

[0061] In this application, "reactive emulsifier" refers to an emulsifying dispersant having radical reactivity, that is, a surfactant having one or more polymerizable unsaturated groups in its molecule, which can be copolymerized with monomers such as (meth)acrylic acid esters.

[0062] Furthermore, "HLB" refers to the HLB value calculated using the Griffin method, where the ethyleneoxy groups in the reactive emulsifier are considered hydrophilic groups.

[0063] The HLB of the compounds (A4-1) to (A4-3) described above is 7 to 18, and 9 to 15 is preferred in terms of emulsion stability (hereinafter simply referred to as emulsion stability) in the composition during emulsion polymerization or dispersion polymerization of the acrylic compounds and after polymerization. Furthermore, it is more preferable to use two or more reactive emulsifiers (A4) having different HLBs within the above range in combination in terms of storage stability of the water-repellent composition.

[0064] In the above general formula (A4-1), R 3 is a hydrogen or methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A1) and / or component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsification stability of the acrylic compound. Y 1 Y is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. 1 The type, combination, and number of alkylene oxy groups in the compound can be appropriately selected within the above HLB range. Furthermore, if there are two or more alkylene oxy groups, they may have a block addition structure or a random addition structure.

[0065] As the compound represented by the above general formula (A4-1), the compound represented by the following general formula (A4-1-1) is preferred.

[0066] [ka] [In formula (A4-1-1), R 3 A is a hydrogen or methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and A 1 O is an alkylene oxy group having 2 to 4 carbon atoms, and m can be appropriately selected within the above HLB range, specifically an integer from 1 to 80 is preferred, and when m is 2 or more there are m A 1 O may be the same or different.

[0067] In the compound represented by the above general formula (A4-1-1), R 3A is a hydrogen or methyl group, and is more preferably a methyl group in terms of copolymerizability with component (A1) and / or component (A2). X is a linear or branched alkylene group having 1 to 6 carbon atoms, and is more preferably a linear alkylene group having 2 to 3 carbon atoms in terms of emulsification stability of the acrylic compound. 1 O is an alkylene oxy group with 2 to 4 carbon atoms. 1 The type and combination of O, and the number of m, can be appropriately selected so as to be within the above HLB range. In terms of emulsification stability of the acrylic compound, m is preferably an integer from 1 to 80, and more preferably an integer from 1 to 60. When m is 2 or more, m A 1 O may be the same or different. Also, A 1 If there are two or more types of oxygen, they can have a block-type or random-type structure.

[0068] The reactive emulsifier represented by the above general formula (A4-1-1) can be obtained by conventionally known methods and is not particularly limited. It can also be more readily obtained than commercially available products, for example, "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0069] In the above general formula (A4-2), R 4 This is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. Examples of such unsaturated hydrocarbon groups include tridecenyl group, tridecadienyl group, tetradecenyl group, tetradienyl group, pentadecenyl group, pentadecadrienyl group, pentadecadrienyl group, heptadecenyl group, heptadecadienyl group, heptadecadrienyl group, etc. In terms of emulsification stability of acrylic compounds, R 4 A monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms is more preferable.

[0070] Y 2 Y is a divalent group containing an alkylene oxy group with 2 to 4 carbon atoms. 2The type, combination, and number of alkylene oxy groups in the compound can be appropriately selected to stay within the above HLB range. Furthermore, if there are two or more alkylene oxy groups, they can have a block addition structure or a random addition structure. In terms of emulsification stability of the acrylic compound, the alkylene oxy group is more preferably an ethylene oxy group.

[0071] As the compound represented by the above general formula (A4-2), the compound represented by the following general formula (A4-2-1) is preferred.

[0072] [ka] [In formula (A4-2-1), R 4 A is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and possessing a polymerizable unsaturated group. 2 O is an alkylene oxy group having 2 to 4 carbon atoms, and n can be appropriately selected within the above HLB range, specifically an integer from 1 to 50 is preferred, and when n is 2 or more, there are n A 2 O may be the same or different.

[0073] In the compound represented by the above general formula (A4-2-1), R 4 This is R in the general formula (A4-2) mentioned above. 4 Similar examples include the above.

[0074] A 2 O is an alkylene oxy group with 2 to 4 carbon atoms. In terms of emulsification stability of acrylic compounds, A 2 The type and combination of O, and the number of n, can be appropriately selected so as to be within the above HLB range. In terms of emulsification stability of acrylic compounds, A 2 O is more preferably an ethylene oxy group, n is preferably an integer from 1 to 50, more preferably an integer from 5 to 20, and even more preferably an integer from 8 to 14. When n is 2 or more, there are n A 2 O may be the same or different. Also, A 2If there are two or more types of oxygen, they can have a block-type or random-type structure.

[0075] The reactive emulsifier represented by the above general formula (A4-2-1) can be synthesized, for example, by adding an alkylene oxide to a phenol having the corresponding unsaturated hydrocarbon group, but is not limited to this. For example, it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120-170°C using an alkaline catalyst such as caustic soda or caustic potassium.

[0076] The phenols having the corresponding unsaturated hydrocarbon groups mentioned above include not only industrially produced pure products or mixtures, but also those that exist as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, and 3-[11(Z)-pentadecenyl]phenol, which are extracted from cashew nut shells, etc., and collectively known as cardanol.

[0077] Compound (A4-3) is obtained by adding a C2-C4 alkylene oxide to an oil or fat having an HLB of 7-18 and containing a hydroxyl group and a polymerizable unsaturated group. Examples of oils and fats containing a hydroxyl group and a polymerizable unsaturated group include mono or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.). In terms of emulsification stability of acrylic compounds, alkylene oxide adducts of fatty acid triglycerides containing at least one hydroxyunsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides 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 number of moles of alkylene oxide added can be appropriately selected to be within the above HLB range, and in terms of emulsification stability of acrylic compounds, 20 to 50 moles are more preferred, and 25 to 45 moles are even more preferred. Also, if there are two or more types of alkylene oxide, they may have a block adduct structure or a random adduct structure.

[0078] Compound (A4-3) can be synthesized, for example, by adding alkylene oxide to oils and fats having hydroxyl groups and polymerizable unsaturated groups, but is not limited to this. For example, it can be synthesized by adding a predetermined amount of alkylene oxide to a triglyceride of a fatty acid containing ricinoleic acid, i.e., castor oil, under pressure at 120-170°C using an alkaline catalyst such as caustic soda or caustic potassium.

[0079] The monomer content of component (A4) in 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, relative to the total amount of monomer components constituting the acrylic compound, from the viewpoint of improving water repellency and emulsion stability in the composition during emulsion polymerization or dispersion polymerization of the acrylic compound and after polymerization.

[0080] Acrylic compounds may contain, in addition to component (A1) and any component (A2), at least one second (meth)acrylic acid ester monomer (A5) (hereinafter also referred to as "component A5") selected from the group consisting of monomers represented by the following general formula (A5-1), monomers represented by the following general formula (A5-2), monomers represented by the following general formula (A5-3), and monomers represented by the following general formula (A5-4) as a monomer component, in order to improve durable water repellency.

[0081] [ka] [In formula (A5-1), R 5 R is a hydrogen or methyl group, 6 This is a monovalent, chain-like hydrocarbon group having 1 to 11 carbon atoms, having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. However, the number of (meth)acryloyloxy groups within the molecule is 2 or less.

[0082] [ka] [In formula (A5-2), R 7 R is a hydrogen or methyl group, 8 This is a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms, which may have substituents.

[0083] [ka] [In formula (A5-3), R 9It is an unsubstituted, monovalent, chain-like hydrocarbon group having 1 to 4 carbon atoms.

[0084] [ka] [In formula (A5-4), R 10 [where p is a hydrogen or methyl group, p is an integer of 2 or more, S is a (p+1) valent organic group, and T is a monovalent organic group having a polymerizable unsaturated group.]

[0085] The monomer (A5-1) described above is a (meth)acrylic acid ester monomer having a monovalent linear hydrocarbon group having 1 to 11 carbon atoms, with the ester portion having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group. From the viewpoint of being receptive to crosslinking agents, it is preferable that the monovalent linear hydrocarbon group having 1 to 11 carbon atoms has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When an acrylic compound containing the monomer (A5-1) having these receptive groups to crosslinking agents is treated with a crosslinking agent on a textile product, the durable water repellency of the resulting textile product can be improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0086] The above-mentioned linear hydrocarbon group may be linear or branched, and may be saturated or unsaturated hydrocarbon group. Furthermore, the linear hydrocarbon group may have substituents in addition to the above-mentioned functional group. Among these, being linear and / or a saturated hydrocarbon group is preferable in that it can improve durable water repellency.

[0087] Specific examples of monomers for (A5-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used individually or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred for their ability to improve durable water repellency. Furthermore, dimethylaminoethyl (meth)acrylate is preferred for its ability to improve texture.

[0088] The amount of component (A5-1) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, based on the total mass of component (A1) and component (A2) of 100 mass, from the viewpoint of water repellency. The amount of component (A5-1) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, based on the total mass of component (A1) and component (A2) of 100 mass, from the viewpoint of water repellency.

[0089] The monomer described in (A5-2) above is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group with 1 to 11 carbon atoms in the ester portion. Examples of cyclic hydrocarbon groups include isobornyl, cyclohexyl, and dicyclopentanyl groups. These cyclic hydrocarbon groups may have substituents such as alkyl groups. However, if the substituent is a hydrocarbon group, a hydrocarbon group is selected such that the sum of the number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. Furthermore, it is preferable from the viewpoint of improving durable water repellency that these cyclic hydrocarbon groups are directly bonded to the ester bond. The cyclic hydrocarbon group may be alicyclic or aromatic, and in the case of alicyclic, it may be a saturated or unsaturated hydrocarbon group. Specific examples of monomers include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. These monomers may be used individually or in combination of two or more. Among these, isobornyl (meth)acrylate and cyclohexyl methacrylate are preferred for their ability to improve durable water repellency, with isobornyl methacrylate being more preferred.

[0090] The amount of component (A5-2) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency. The amount of component (A5-2) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency.

[0091] The monomer described above (A5-3) is a methacrylate ester monomer in which an unsubstituted, monovalent, chain-like hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester portion. Preferred chain-like hydrocarbon groups having 1 to 4 carbon atoms include straight-chain hydrocarbon groups having 1 to 2 carbon atoms and branched hydrocarbon groups having 3 to 4 carbon atoms. Examples of chain-like hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used individually or in combination of two or more. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred for their ability to improve durable water repellency, with methyl methacrylate being more preferred.

[0092] The amount of component (A5-3) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency. The amount of component (A5-3) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency.

[0093] The monomer of (A5-4) described above is a (meth)acrylic acid ester monomer having three or more polymerizable unsaturated groups in one molecule. A polyfunctional (meth)acrylic acid ester monomer having three or more (meth)acryloyloxy groups in one molecule, in which T in the above general formula (A5-4) is a (meth)acryloyloxy group, is preferred. In formula (A5-4), the p Ts may be the same or different. Specific compounds include, for example, ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. These monomers may be used individually or in combination of two or more. Among these, tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred because they can improve durable water repellency.

[0094] The amount of component (A5-4) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency. The amount of component (A5-4) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the total mass of component (A1) and component (A2) to be added, from the viewpoint of water repellency.

[0095] In an acrylic compound, the total composition ratio of the monomers of component (A5) described above is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass, relative to the total amount of monomer components constituting the acrylic compound, from the viewpoint of water repellency and texture.

[0096] The amount of component (A5) to be added is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total mass of components (A1) and (A2) to be added, from the viewpoint of water repellency. The amount of component (A5) to be added is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the total mass of components (A1) and (A2) to be added, from the viewpoint of water repellency.

[0097] The acrylic compound may contain, in addition to component (A1) and any component (A2), a monofunctional monomer (A6) copolymerizable with these components (hereinafter also referred to as "component (A6)"), to the extent that it does not impair the effects of the present invention.

[0098] Examples of component (A6) include (meth)acryloylmorpholine, (meth)acrylic acid esters having hydrocarbon groups other than those listed in (A1), (A2), and (A5), (meth)acrylic acid, fumarate esters, maleate esters, fumarate, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers other than component (A3) that do not contain fluorine. Note that (meth)acrylic acid esters having hydrocarbon groups other than components (A1), (A2), and (A5) may have substituents on the hydrocarbon group such as vinyl groups, hydroxyl groups, amino groups, epoxy groups, isocyanate groups, blocked isocyanate groups, etc., and may also have substituents other than groups that can react with crosslinking agents such as quaternary ammonium groups, and may have ether bonds, ester bonds, amide bonds, or urethane bonds. Examples of (meth)acrylic acid esters 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 because it can improve the peel strength of the coating on the resulting textile product.

[0099] The mass of component (A6) to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the total mass of components (A1) and (A2) to be blended, from the viewpoint of water repellency. The mass of the monomer of (A6) to be blended is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less, relative to 100 parts by mass of the total mass of components (A1) and (A2) to be blended, from the viewpoint of water repellency.

[0100] Acrylic compounds are preferably found to have at least one functional group selected from the group consisting of hydroxyl groups, amino groups, carboxyl groups, epoxy groups, and isocyanate groups that can react with a crosslinking agent, as this improves durable water repellency. The isocyanate groups may form blocked isocyanate groups protected by a blocking agent. Furthermore, acrylic compounds are preferably found to have amino groups, as this improves texture.

[0101] The weight-average molecular weight of the acrylic compound is preferably 30,000 or more. A weight-average molecular weight of 30,000 or more tends to further improve water repellency. Furthermore, a weight-average molecular weight of 50,000 or more is even more preferable. In this case, water repellency can be achieved more effectively. The upper limit of the weight-average molecular weight of the acrylic compound is preferably around 5 million.

[0102] The weight-average molecular weight of acrylic compounds is measured using a GPC instrument (Tosoh Corporation's GPC "HLC-8020") under conditions of a column temperature of 40°C and a flow rate of 1.0 ml / min, using tetrahydrofuran as the eluent, and the value is expressed in terms of standard polystyrene. The column used is a combination of three columns from Tosoh Corporation, product names TSK-GELG5000HHR, G4000HHR, and G3000HHR.

[0103] The melt viscosity of the acrylic compound at 105°C is preferably 1000 Pa·s or less. When the melt viscosity at 105°C is 1000 Pa·s or less, it tends to be easier to maintain a good texture. Furthermore, when the melt viscosity of the acrylic compound is 1000 Pa·s or less, it is possible to suppress the precipitation or sedimentation of the acrylic compound when it is emulsified or dispersed to form a water-repellent composition, thus tending to improve the storage stability of the water-repellent composition. More preferably, the melt viscosity at 105°C is 500 Pa·s or less. In this case, sufficient water repellency is achieved while also having a superior texture.

[0104] "Melting viscosity at 105°C" is determined by using an elevated flow tester (e.g., Shimadzu CFT-500), placing 1 g of non-fluorinated polymer into a cylinder fitted with a die (10 mm long, 1 mm in diameter), holding it at 105°C for 6 minutes, and measuring the viscosity using a plunger at 100 kg·f / cm². 2 This refers to the viscosity measured when a load is applied.

[0105] (Silicone-based compounds) The silicone-based compound is, for example, at least one of silicone resin and silicone oil. Among such silicone-based compounds, silicone resin is preferred from the viewpoint of water repellency. The silicone-based compound may be used alone or in combination of two or more types.

[0106] The silicone resin may be an organopolysiloxane having a three-dimensional structure, solid at 25°C, and containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as constituent components. Here, M, D, T, and Q are (R'')3SiO 0.5 Units: (R'')2SiO, R''SiO 1.5 This represents units and SiO2 units. R'' represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.

[0107] Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have portions indicated as MDQ, MTQ, or MDTQ.

[0108] Silicone resin can also be obtained as a solution obtained by dissolving it in a suitable solvent. Examples of solvents include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents.

[0109] Examples of silicone resin solutions include KF7312J (trimethylsilyl group-containing polysiloxane:decamethylcyclopentasiloxane = 50:50 mixture), KF7312F (trimethylsilyl group-containing polysiloxane:octamethylcyclotetrasiloxane), KF9021L (trimethylsilyl group-containing polysiloxane:low viscosity methylpolysiloxane = 50:50 mixture), and KF7312L (trimethylsilyl group-containing polysiloxane:low viscosity methylpolysiloxane = 50:50 mixture), all commercially available from Shin-Etsu Chemical Co., Ltd.

[0110] Examples of silicone resins alone include MQ-1600solidResin (trimethylsilyl group-containing polysiloxane) and MQ-1640FlakeResin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), both commercially available from Toray Dow Corning Co., Ltd. The above-mentioned commercially available products contain trimethylsilyl group-containing polysiloxane and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0111] Silicone oils are linear organopolysiloxanes, and may have organic groups in at least one of the side chains and terminals of the organopolysiloxane. Such silicone oils can be the same as hydrophobic silicone oils and functionalized silicone oils, and examples include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; and modified silicone oils such as amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, and higher aliphatic amide-modified silicone oil.

[0112] Examples of amino-modified silicone oils include compounds having an organic group containing an amino group and / or an imino group in at least one of the side chains and / or terminals of an organopolysiloxane. Examples of such organic groups include organic groups represented as -R-NH2 and organic groups represented as -R-NH-R'-NH2. Examples of R and R' include divalent groups such as ethylene groups and propylene groups. Some or all of the amino groups and / or imino groups may be chelated amino groups and / or imino groups. Chelated amino groups and / or imino groups can be obtained, for example, by treating the amino groups and / or imino groups with a chelating agent. Examples of chelating agents include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

[0113] From the viewpoint of water repellency, the functional group equivalent of the amino-modified silicone oil is preferably 100 to 20,000 g / mol, more preferably 150 to 12,000 g / mol, and even more preferably 200 to 4,000 g / mol.

[0114] The amino-modified silicone oil is preferably liquid at 25°C. The kinematic viscosity of the amino-modified silicone oil at 25°C is 10 to 100,000 mm². 2 It is preferable that the value be / s, and the range is 10 to 30,000 mm. 2 It is more preferable that it be / s, and 10 to 5,000 mm 2 It is even more preferable that the kinematic viscosity at 25°C is 100,000 mm². 2 If the value is greater than / s, the viscosity tends to be too high, resulting in poor workability. The kinematic viscosity at 25°C refers to the value measured using the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0115] Amino-modified silicone oils are readily available as commercial products. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, KF-8021 (all manufactured by Shin-Etsu Chemical Co., Ltd., product names), TSF-4709, XF42-B1989 (manufactured by Momentive Performance Materials Japan LLC, product name), BY16-872, SF-8417, BY16-853U, BY16-892 (all manufactured by Toray Dow Corning Co., Ltd., product names), KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd.), and WACKER® FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicone).

[0116] In addition, silicone oils other than amino-modified silicone oils are also readily available as commercial products. Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., product name, carboxyl-modified silicone oil), SF8428 (manufactured by Toray Dow Corning Co., Ltd., product name, carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., product name, methyl hydrogen silicone oil), and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., product name). Examples include high-grade fatty acid ester-modified silicone oil, KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., product name, dimethyl silicone oil), SF8416 (manufactured by Toray Dow Corning Co., Ltd., product name, alkyl-modified silicone oil), SH203 (manufactured by Toray Dow Corning Co., Ltd., product name, alkyl aralkyl-modified silicone oil), and SF8410 (manufactured by Toray Dow Corning Co., Ltd., product name, polyether-modified silicone oil).

[0117] The silicone compound may be an organo-modified silicone represented by the following general formula (1). In the following general formula (1), each structural unit may be a block, randomly arranged, or arranged alternately.

[0118] [ka] [In formula (1), R 20 , R 21 and R 22 Each of these is independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R 23 R is a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 8 to 40 carbon atoms. 30 , R 31 , R 32 , R 33 , R 34 and R 35Each of these 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 22 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 between 10 and 200, and if a is 2 or greater, there are multiple R 20 and R 21 These can be the same or different, and if b is 2 or more, there can be multiple R 22 and R 23 These may be the same or different.

[0119] In organo-modified silicones, the above-mentioned alkoxyl groups having 1 to 4 carbon atoms may be linear or branched. Examples of alkoxyl groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups. In terms of being easy to manufacture industrially and readily available, R 20 , R 21 and R 22 Each of these is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

[0120] Examples of the above-mentioned hydrocarbon groups having 8 to 40 carbon atoms and having an aromatic ring include aralkyl groups having 8 to 40 carbon atoms and groups represented by the following general formulas (2) or (3).

[0121] [ka] [In formula (2), R 40 R is an alkylene group having 2 to 6 carbon atoms. 41 R is a single bond or an alkylene group with 1 to 4 carbon atoms, where c is an integer from 0 to 3. If c is 2 or 3, there are multiple R groups. 41 They may be the same or different.

[0122] The alkylene group described above may be linear or branched.

[0123] [ka] [In formula (3), R 42 R is an alkylene group having 2 to 6 carbon atoms. 43 R is a single bond or an alkylene group with 1 to 4 carbon atoms, and d is an integer from 0 to 3. If d is 2 or 3, there are multiple R groups. 43 They may be the same or different.

[0124] The alkylene group described above may be linear or branched.

[0125] Examples of the above-mentioned aralkyl groups having 8 to 40 carbon atoms include phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, phenylhexyl group, and naphthylethyl group. Among these, phenylethyl group and phenylpropyl group are preferred because they are easy to manufacture industrially and readily available.

[0126] In the group represented by the above general formula (2), R is easy to manufacture industrially and readily available. 40 It is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0.

[0127] In the group represented by the above general formula (3), R is easy to manufacture industrially and readily available. 42 is preferably an alkylene group having 2 to 4 carbon atoms, and d is preferably 0 or 1, and more preferably 0.

[0128] As for the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring as described above, the aralkyl group having 8 to 40 carbon atoms and the group represented by the general formula (2) are preferred in that they are easy to manufacture industrially and readily available, and the aralkyl group having 8 to 40 carbon atoms is more preferred in that it can improve water repellency.

[0129] The above alkyl group having 8 to 40 carbon atoms may be linear or branched. Examples of the alkyl group having 8 to 40 carbon atoms include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, cetyl group, stearyl group, behenyl group, hexacosyl group, octacosyl group, triacontyl group, dotriacontyl group, and the like. As the alkyl group having 8 to 40 carbon atoms, an alkyl group having 12 to 36 carbon atoms is preferred, and an alkyl group having 16 to 34 carbon atoms is more preferred, from the viewpoint of improving water repellency. It should be noted that alkyl groups with fewer carbon atoms tend to provide better chalk mark performance. Furthermore, alkyl groups with more carbon atoms tend to provide better water repellency. In addition, when 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 8, water repellency tends to be poor.

[0130] In the organo-modified silicone, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms having an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. From the viewpoints of ease of industrial production and ready availability, R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are each independently preferably a hydrogen atom, a methyl group, an ethyl group or an alkoxy group having 1 to 4 carbon atoms, and a methyl group is more preferred among these.

[0131] In the organo-modified silicone, a is an integer of 0 or more. From the viewpoints of ease of industrial production, ready availability, and more excellent peel strength, a is preferably 40 or less, and more preferably 30 or less.

[0132] In organo-modified silicones, (a+b) is between 10 and 200. Preferably, (a+b) is between 20 and 100, and more preferably between 40 and 60, as this facilitates industrial manufacturing and availability. When (a+b) falls within this range, the silicone itself tends to be easier to manufacture and handle.

[0133] Organo-modified silicones can be synthesized by conventionally known methods. For example, organo-modified silicones can be obtained by hydrosilylation of a silicone having a SiH group with an aromatic compound having a vinyl group and / or an α-olefin.

[0134] Examples of silicones having the SiH group mentioned above include methyl hydrogen silicone with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methyl hydrogen siloxane. Among these, methyl hydrogen silicone is preferred because it is easy to manufacture industrially and readily available.

[0135] The above aromatic compounds having a vinyl group are R in the above general formula (1). 23 In this context, it refers to compounds from which hydrocarbon groups having 8 to 40 carbon atoms and possessing an aromatic ring are derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allylphenyl ether, allylnaphthyl ether, allyl-p-cumylphenyl ether, allyl-o-phenylphenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0136] The above α-olefin is R in the above general formula (1). 23In this context, it is a compound from which alkyl groups having 8 to 40 carbon atoms are derived. Examples of α-olefins include 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacocene (C28), 1-triaconthene (C30), and 1-dotriaconthene (C32), all of which have 8 to 40 carbon atoms.

[0137] The above hydrosilylation reaction may be carried out by reacting the above-mentioned silicone having the SiH group with the above-mentioned aromatic compound having the vinyl group and the above-mentioned α-olefin in a stepwise or all-at-a-time manner, in the presence of a catalyst as needed.

[0138] The amounts used in the hydrosilylation reaction of the silicone having SiH groups, the aromatic compound having vinyl groups, and the α-olefin can be appropriately selected depending on the SiH group equivalent of the silicone having SiH groups, or the number-average molecular weight, etc.

[0139] Examples of catalysts used in hydrosilylation reactions include compounds such as platinum and palladium, with platinum compounds being preferred. Examples of platinum compounds include platinum(IV) chloride.

[0140] The reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate. The reaction temperature is, for example, 10 to 200°C, preferably 50 to 150°C. The reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.

[0141] Furthermore, the hydrosilylation reaction is preferably carried out under an inert gas atmosphere. Examples of inert gases include nitrogen and argon. The reaction will proceed even without a solvent, but a solvent may be used. Examples of solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.

[0142] As a non-fluorine-based water-repellent component, it is preferable to use the above-mentioned acrylic compound and the above-mentioned silicone compound in combination, from the viewpoint of water repellency and chalk mark resistance. The mass ratio of the acrylic compound (α) to the silicone compound (β) is not particularly limited. For example, if the silicone compound (β) is a silicone resin, the total of the acrylic compound (α) and the silicone compound (β) may be 100 parts by mass, with the silicone compound (β) accounting 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. When the proportion of the silicone compound (β) is within this range, excellent water repellency and Bundesmann water repellency after wear are achieved. Alternatively, if the silicone compound (β) is an organo-modified silicone, the total of the acrylic compound (α) and the silicone compound (β) may be 100 parts by mass, with the silicone compound (β) accounting for 10 to 90 parts by mass. Preferably, the amount is 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass. Having the proportion of silicone compound (β) within this range results in excellent water repellency and reduced chalk marks.

[0143] (Wax-based compounds) The wax-based compound is, for example, at least one selected from paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, animal and plant waxes, and mineral waxes, and paraffin wax is preferred from the viewpoint of water repellency, durable water repellency, and texture.

[0144] The wax-based compound may be, for example, one or both of n-alkanes and n-alkenes. From the viewpoint of water repellency, durable water repellency, and texture, the wax-based compound is preferably a n-alkane.

[0145] Examples of normal alkanes include at least one selected from tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, and hexatriacontane. From the viewpoint of water repellency, durable water repellency, and texture, the normal alkane is preferably triacontane, hentriacontane, or dotriacontane.

[0146] Examples of normal alkenes include at least one selected from 1-eicosene, 1-docosene, 1-trichosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosene, triacontene, hentriacontene, dotriacontene, tritriacontene, tetratriacontene, pentatriacontene, and hexatriacontene. From the viewpoint of water repellency, durable water repellency, and texture, the normal alkene is preferably at least one of triacontene, hentriacontene, and dotriacontene.

[0147] The number of carbon atoms in the wax compound is not particularly limited, but may be between 20 and 60, and is preferably between 25 and 45 from the viewpoint of water repellency, durable water repellency, and texture.

[0148] The weight-average molecular weight of the wax compound is not particularly limited, but may be between 300 and 850, and is preferably between 300 and 700 from the viewpoint of water repellency, durable water repellency, and texture.

[0149] The melting point of the wax-based compound is preferably 35 to 90°C, more preferably 40 to 85°C, even more preferably 45 to 80°C, and even more preferably 50 to 75°C, from the viewpoint of good water repellency and durable water repellency, particularly with respect to cotton. The melting point of the wax-based compound refers to the value measured by the same method as in JIS K2235-1991.

[0150] The penetration degree of the wax compound is not particularly limited, but may be, for example, 30 or less, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less, from the viewpoint of water repellency and durable water repellency. The penetration degree of the wax compound is not particularly limited, but may be, for example, 0.1 or more, and may be 1 or more. The penetration degree of the wax compound refers to the value measured by the same method as in JIS K2235-1991.

[0151] (Urethane-based compounds) Urethane 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, (U1) Aliphatic polyisocyanate derivatives with an average of 2 or more isocyanate groups, (U2) A long-chain active hydrogen compound having both a hydrocarbon group with 12 to 30 carbon atoms and an active hydrogen group, (U3) Cationic active hydrogen compounds having both an active hydrogen group and a cationic group, (U4) A cationic group and an acid compound that forms a salt, The reaction product may be the above. Here, the concentration of the hydrocarbon group may be 30% or more and 85% or less. Furthermore, the aliphatic polyisocyanate derivative may include an isocyanurate derivative of aliphatic polyisocyanate. In addition, in the cationic active hydrogen compound, the cationic group may be a tertiary amino group, the active hydrogen group may be a hydroxyl group, and the cationic active hydrogen compound may have two or more hydroxyl groups per molecule. When the urethane compound is a reaction product obtained using a long-chain active hydrogen compound and the concentration of the hydrocarbon group is in a predetermined proportion, it tends to have excellent water repellency. Furthermore, when the urethane compound is a reaction product obtained using a cationic active hydrogen compound, for example, the affinity with fibers is improved, which tends to improve washing durability.

[0152] Examples of aliphatic polyisocyanates that constitute the aliphatic polyisocyanate derivative (U1) include aliphatic diisocyanates such as hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. In this application, "aliphatic polyisocyanate" is a concept that includes alicyclic polyisocyanates.

[0153] Examples of alicyclic polyisocyanates include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexyl isocyanate) or mixtures thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0154] The aliphatic polyisocyanate is preferably one or both of hexamethylene diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane (hereinafter simply referred to as bis(isocyanatomethyl)cyclohexane), and more preferably hexamethylene diisocyanate.

[0155] Examples of aliphatic polyisocyanate derivatives include polymers of the above-mentioned aliphatic polyisocyanates (e.g., dimers, trimers (e.g., isocyanurate derivatives, iminooxadiazinedione derivatives), pentamers, heptamers, etc.), allophanate derivatives (e.g., allophanate derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with a monohydric alcohol or a dihydric alcohol), polyol derivatives (e.g., polyol derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with a trihydric alcohol (e.g., trimethylolpropane, etc.) (alcohol adducts, preferably trimethylolpropane) Examples include pan adducts, biuret derivatives (for example, biuret derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with water or amines), urea derivatives (for example, urea derivatives produced by the reaction of the above-mentioned aliphatic polyisocyanate with diamines), oxadiazinetrione derivatives (for example, oxadiazinetrione produced by the reaction of the above-mentioned aliphatic polyisocyanate with carbon dioxide), carbodiimide derivatives (for example, carbodiimide derivatives produced by the decarboxylation condensation reaction of the above-mentioned aliphatic polyisocyanate), uretdione derivatives, uretonimine derivatives, and the like.

[0156] The aliphatic polyisocyanate derivative is preferably at least one of isocyanurate derivatives, trimethylolpropane adducts, allophanate derivatives, and biuret derivatives, and more preferably an isocyanurate derivative. When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture is improved.

[0157] The aliphatic polyisocyanate derivative is more preferably at least one of the following: an isocyanurate derivative of hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, a biuret derivative of hexamethylene diisocyanate, and an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, and even more preferably an isocyanurate derivative of hexamethylene diisocyanate.

[0158] Aliphatic polyisocyanate derivatives can be used individually or in combination of two or more. Preferably, an isocyanurate derivative of hexamethylene diisocyanate can be used alone, or an isocyanurate derivative of hexamethylene diisocyanate can be used in combination with at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. In this case, the proportion of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or less, relative to 100 parts by mass of the total amount of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of isocyanurate derivatives of bis(isocyanatomethyl)cyclohexane, trimethylolpropane adduct of hexamethylene diisocyanate, allophanate derivative of hexamethylene diisocyanate, and biuret derivative of hexamethylene diisocyanate. Preferably, the amount is 70 parts by mass or more, and also, for example, 85 parts by mass or less. Furthermore, the blending ratio of at least one selected from the group consisting of isocyanurate derivatives of bis(isocyanatomethyl)cyclohexane, trimethylolpropane adducts of hexamethylene diisocyanate, allophanate derivatives of hexamethylene diisocyanate, and biuret derivatives of hexamethylene diisocyanate is, for example, 15 parts by mass or more, and also, for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0159] Aliphatic polyisocyanate derivatives can be produced by known methods.

[0160] The average number of isocyanate groups in an aliphatic polyisocyanate derivative is 2 or more, preferably 2.5, more preferably 2.9, and for example, 3.8 or less. If the average number of isocyanate groups is above the lower limit, the water repellency can be further improved. The average number of isocyanate groups is calculated from the isocyanate group concentration A, solid content concentration B, and the number-average molecular weight C measured by gel permeation chromatography using the following apparatus and conditions, using the following formula (1). Furthermore, when two or more aliphatic polyisocyanate derivatives are used in combination, the average number of isocyanate groups is calculated based on the weight ratio of the aliphatic polyisocyanate derivatives and their average number of isocyanate functional groups.

[0161] Average number of isocyanate functional groups = A / B × C / 42.02 (1) (In the formula, A represents the isocyanate group concentration of the aliphatic polyisocyanate derivative, B represents the solids content concentration, and C represents the number-average molecular weight.)

[0162] (Measurement conditions for number-average molecular weight) Equipment: HLC-8220GPC (manufactured by Tosoh) Columns: TSKgelG1000HXL, TSKgelG2000HXL, and TSKgelG3000HXL (manufactured by Tosoh) connected in series. Detector: Differential refractometer Injection volume: 100μL Eluent: Tetrahydrofuran Flow rate: 0.8mL / min Temperature: 40℃ Calibration curve: Standard polyethylene oxide in the range of 10⁶ to 22450 (manufactured by Tosoh Corporation, product name: TSK Standard Polyethylene Oxide)

[0163] Long-chain active hydrogen compounds possess both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.

[0164] The hydrocarbon group having 12 to 30 carbon atoms may be, for example, a linear or branched saturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkyl group), or a linear or branched unsaturated hydrocarbon group having 12 to 30 carbon atoms (e.g., an alkenyl group).

[0165] The active hydrogen group may be, for example, a hydroxyl group.

[0166] Such long-chain active hydrogen compounds having both hydrocarbon groups and active hydrogen groups may be, for example, at least one of the following: linear saturated hydrocarbon group-containing active hydrogen compounds, branched saturated hydrocarbon group-containing active hydrogen compounds, linear unsaturated hydrocarbon group-containing active hydrogen compounds, and branched unsaturated hydrocarbon group-containing active hydrogen compounds.

[0167] A linear saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear saturated hydrocarbon group having 12 to 30 carbon atoms, and examples include linear saturated hydrocarbon group-containing alcohols such as n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, and eicosanol, as well as linear saturated hydrocarbon group-containing sorbitan esters such as sorbitan tristearate.

[0168] Branched-chain saturated hydrocarbon group-containing active hydrogen compounds are active hydrogen compounds containing branched-chain saturated hydrocarbon groups having 12 to 30 carbon atoms, and examples include branched-chain saturated hydrocarbon group-containing alcohols such as isomiristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol.

[0169] A linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear unsaturated hydrocarbon group having 12 to 30 carbon atoms, and examples include linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, eicocenyl alcohol, dococenyl alcohol, tetracocenyl alcohol, hexacocenyl alcohol, and octacocenyl alcohol.

[0170] A branched-chain unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain unsaturated hydrocarbon group having 12 to 30 carbon atoms, such as phytol.

[0171] The long-chain active hydrogen compound is preferably one or both of a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound. The long-chain active hydrogen compound can be used alone or in combination of two or more types.

[0172] When using long-chain active hydrogen compounds alone, preferably, a linear saturated hydrocarbon group-containing active hydrogen compound is used alone; more preferably, a linear saturated hydrocarbon group-containing alcohol is used alone; and even more preferably, stearyl alcohol is used alone. When using two or more long-chain active hydrogen compounds in combination, preferably, a linear saturated hydrocarbon group-containing active hydrogen compound and a linear unsaturated hydrocarbon group-containing active hydrogen compound are used in combination; more preferably, a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol are used in combination; or a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester, and a linear unsaturated hydrocarbon group-containing alcohol are used in combination.

[0173] When using a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 40 parts by mass or more, preferably 55 parts by mass or more, and more preferably 70 parts by mass or more, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 60 parts by mass or less, preferably 45 parts by mass or less, and more preferably 30 parts by mass or less, based on 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol and the linear unsaturated hydrocarbon group-containing alcohol. If the blending ratio of the linear saturated hydrocarbon group-containing alcohol is above the above lower limit, the crystallinity of the hydrocarbon group is improved, and as a result, the water repellency can be improved.

[0174] When using a linear saturated hydrocarbon group-containing alcohol, a linear saturated hydrocarbon group-containing sorbitan ester, and a linear unsaturated hydrocarbon group-containing alcohol in combination, the blending ratio of the linear saturated hydrocarbon group-containing alcohol is, for example, 30 parts by mass or more, and for example, 60 parts by mass or less, per 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. The blending ratio of the linear saturated hydrocarbon group-containing sorbitan ester is, for example, 20 parts by mass or more, and for example, 50 parts by mass or less, per 100 parts by mass of the total amount of the linear saturated hydrocarbon group-containing alcohol, the linear saturated hydrocarbon group-containing sorbitan ester, and the linear unsaturated hydrocarbon group-containing alcohol. Furthermore, the proportion of the linear unsaturated hydrocarbon group-containing alcohol is, for example, 10 parts by mass or more, and for example, 20 parts by mass or less, based on 100 parts by mass of the total amount of linear saturated hydrocarbon group-containing alcohol, linear saturated hydrocarbon group-containing sorbitan ester, and linear unsaturated hydrocarbon group-containing alcohol.

[0175] When two or more long-chain active hydrogen compounds are used in combination, it is even more preferable to use a linear saturated hydrocarbon group-containing alcohol and a linear unsaturated hydrocarbon group-containing alcohol in combination, and particularly preferable to use stearyl alcohol and oleyl alcohol in combination.

[0176] Cationic active hydrogen compounds possess both an active hydrogen group and a cationic group. Cationic active hydrogen compounds can be used alone or in combination of two or more types.

[0177] As described above, the active hydrogen group is an active hydrogen group that reacts with an aliphatic polyisocyanate derivative, such as a hydroxyl group. Cationic active hydrogen compounds preferably have two or more hydroxyl groups per molecule. Cationic groups include, for example, tertiary amino groups. In other words, cationic active hydrogen compounds preferably have two or more hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group. More preferably, cationic active hydrogen compounds have two hydroxyl groups per molecule as active hydrogen groups and a tertiary amino group as a cationic group. Such cationic active hydrogen compounds can provide good dispersibility in water and introduce cationic groups that have affinity for fibers, thereby improving washing durability.

[0178] Examples of such cationic active hydrogen compounds include alkyldialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine, with N-methyldiethanolamine being preferred.

[0179] Acid compounds are compounds that form salts with cationic groups. Examples of acid compounds include one or both of organic acids and inorganic acids. Examples of organic acids include acetic acid, lactic acid, tartaric acid, or malic acid, preferably acetic acid or lactic acid, more preferably acetic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, or phosphoric acid, preferably hydrochloric acid. The acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid volatilizes due to heat treatment, which reduces ionicity, improves water resistance, and enhances water repellency. Furthermore, the volatilization of the acid due to heat treatment makes it easier for cationic groups to adsorb to fibers, improving wash durability. Acid compounds can be used alone or in combination of two or more types.

[0180] A urethane compound is obtained as a reaction product by reacting the above-mentioned aliphatic polyisocyanate derivative with a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. To react the aliphatic polyisocyanate derivative with the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound, first, the long-chain active hydrogen compound is added to the aliphatic polyisocyanate derivative, and then the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound are reacted. At this time, the long-chain active hydrogen compound is added such that, for example, if the average number of isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate is 3, then two isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate are modified by the long-chain active hydrogen compound into hydrocarbon groups having 12 to 30 carbon atoms, and one isocyanate group remains in the isocyanurate derivative of the aliphatic polyisocyanate, and no unreacted isocyanurate derivative of the aliphatic polyisocyanate remains. Specifically, a long-chain active hydrogen compound is blended with an aliphatic polyisocyanate derivative such that the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate group / active hydrogen group) is, for example, 1.2 or more, preferably 1.5 or more, and for example, 2.0 or less. As a result, the molecular ends 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) consist of a hydrocarbon group with 12 to 30 carbon atoms and an isocyanate group.

[0181] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions are such that the reaction temperature is, for example, between 70°C and 120°C, and the reaction time is between 1 hour and 6 hours. The above reaction is carried out until the isocyanate concentration of the first intermediate reaction product reaches a predetermined calculated value. The isocyanate concentration can be measured using a potentiometric titrator by the n-dibutylamine method in accordance with JIS K-1556.

[0182] Furthermore, in the above reaction, known solvents such as methyl ethyl ketone can be added in appropriate proportions.

[0183] Next, a cationic active hydrogen compound is added to the reaction solution containing the first intermediate reaction product, and the first intermediate reaction product is reacted with the cationic active hydrogen compound. At this time, the cationic active hydrogen compound is added to the first intermediate reaction product such that the equivalent ratio of isocyanate groups to active hydrogen groups of the cationic active hydrogen compound (isocyanate groups / active hydrogen groups) is, for example, 0.95 or more, and for example, 1.05 or less.

[0184] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions are such that the reaction temperature is, for example, 70°C to 120°C, and the reaction time is 0.5 hours to 4 hours. The above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is complete. In addition, a known solvent such as methyl ethyl ketone may be added in an appropriate proportion to the above reaction. This yields a reaction product between the first intermediate reaction product and the cationic active hydrogen compound (hereinafter referred to as the second intermediate reaction product). The second intermediate reaction product has hydrocarbon groups and cationic groups having 12 to 30 carbon atoms.

[0185] Next, an acid compound is added to the second intermediate reaction product. The proportion of the acid compound is, for example, 0.5 moles or more, preferably 3 moles or more, and also, for example, 10 moles or less, preferably 4 moles or less, per mole of cationic groups of the cationic active hydrogen compound. As a result, the acid compound forms a salt with the cationic groups of the second intermediate reaction product, yielding a reaction solution containing the reaction product (i.e., a urethane-based compound) of the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound. The above reaction product has hydrocarbon groups with 12 to 30 carbon atoms and also has cationic groups. Furthermore, because the above reaction product has hydrocarbon groups with 12 to 30 carbon atoms, it can self-disperse (self-emulsify) in water without the need for a dispersant (emulsifier). In other words, the above reaction product can be internally emulsified.

[0186] Next, while maintaining the temperature of the reaction solution at, for example, between 50°C and 100°C, water is added to the reaction solution to emulsify it. After that, the solvent is removed from the reaction solution. This yields an aqueous dispersion containing the above-mentioned reaction product (i.e., a urethane compound). The solid content concentration of the aqueous dispersion is, for example, 10% by mass or more, and also, for example, 30% by mass or less.

[0187] Because these urethane-based compounds are reaction products obtained using long-chain active hydrogen compounds, they exhibit excellent water repellency, as well as superior oil repellency, oil resistance, and stain resistance. Furthermore, because these urethane-based compounds are reaction products obtained using cationic active hydrogen compounds, their affinity with fibers is improved, resulting in superior wash durability for fibers.

[0188] In such urethane compounds, the concentration of hydrocarbon groups is 30% or more, and 85% or less, preferably 50%. If the concentration of hydrocarbon groups is above the lower limit, water repellency can be improved. If the concentration of hydrocarbon groups is below the upper limit, the stability of the urethane compound can be improved. The concentration of hydrocarbon groups can be calculated from the amount of each component added as described above.

[0189] In the above explanation, first, an aliphatic polyisocyanate derivative is reacted with a long-chain active hydrogen compound to obtain a reaction solution containing a first intermediate reaction product, then the first intermediate reaction product is reacted with a cationic active hydrogen compound to obtain a reaction solution containing a second intermediate reaction product, and then the second intermediate reaction 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, and then the long-chain active hydrogen compound can be reacted with 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 combined and reacted together.

[0190] (Dendrimer compounds) The dendrimer compound may be, for example, a dendritic polymer compound having a radial structure that is regularly branched from the center. For the dendritic polymer compound, those having a linear or branched hydrocarbon group with 1 or more carbon atoms at the terminal branch portion can be used to obtain water repellency.

[0191] As the dendritic polymer compound, for example, "a polymer extender" disclosed in International Publication No. WO 2014 / 160906 can be used. For example, a compound obtained by reacting at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate or mixtures thereof with at least one isocyanate-reactive compound selected from the following formula (Ia), (Ib) or (Ic) can be used.

[0192]

Chemical Formula

[0193] In the above formula, R 50 are each independently -H, R 51 , -C(O)R 51 , -(CH2CH2O) n (CH(CH3)CH2O) m R 52 , or -(CH2CH2O) n (CH(CH3)CH2O) m C(O)R 51 wherein each n is independently 0 to 20, each m is independently 0 to 20, and m+n is greater than 0. In addition, R 51 are each independently a linear or branched alkyl group having 5 to 29 carbon atoms which may optionally contain one or more unsaturated bonds, and R 52 are each independently -H or a linear or branched alkyl group having 6 to 30 carbon atoms which may optionally contain one or more unsaturated bonds.

[0194] Note that in formula (Ia), at least one of R 50 or R 52 is -H.

[0195] In the above formula, R 53 These are -H and -R, respectively, independently. 51 , -C(O)R 51 -(CH2CH2O(CH(CH3)CH2O) m R 52 , or -(CH2CH2O(CH(CH3)CH2OC(O)R 51 And R 54 Each of these may independently contain -H, or one or more unsaturated bonds, a linear or branched alkyl group having 6 to 30 carbon atoms, -(CH2CH2O) n’ (CH(CH3)CH2O) m’ R 52 , or -(CH2CH2O(CH(CH3)CH2OC(O)R 51 Therefore, n' is independently between 0 and 20, m' is independently between 0 and 20, and m+n is greater than 0.

[0196] Note that in equation (Ib), R 52 , R 53 or R 54 At least one of them is -H.

[0197] In the above formula, R 55 -H, -C(O)R 51 , or -CH2C[CH2OR 50 ]3.

[0198] Note that in equation (Ic), R 55 or R 50 At least one of them is -H.

[0199] The isocyanate group-containing compound is not particularly limited, and examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified polyisocyanates such as dimers and trimers thereof. Commercially available products such as "DESMODURN-100" (trade name, manufactured by Bayer), "Duranate THA-100" (trade name, manufactured by Asahi Kasei Corporation), and "Duranate 24A-100" (trade name, manufactured by Asahi Kasei Corporation) can be used. Further, the reaction can be carried out, for example, at 80°C for 1 hour or longer.

[0200] 2.1.2 Other components The water-repellent treatment agent may contain other components such as an aqueous medium and an emulsifier, in addition to the aforementioned non-fluorine-based water-repellent component, for example.

[0201] (Aqueous medium) The aqueous medium may be water or a mixture of water and an organic solvent. The amount of the organic solvent may be, for example, 0.1% by mass or more and 30% by mass or less, or 0.1% by mass or more and 10% by mass or less, relative to the aqueous medium. The aqueous medium preferably consists only of water. The amount of the aqueous medium may be 30 to 99% by mass, or 50 to 90% by mass, based on 100% by mass of the total water-repellent treatment agent.

[0202] (Emulsifier) The water-repellent treatment agent may contain an emulsifier to improve the dispersibility of the non-fluorine-based water-repellent component and the like in the solvent. The emulsifier may be at least one selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. From the viewpoint of water repellency, the emulsifier is preferably a single nonionic surfactant or a combination of a nonionic surfactant and a cationic surfactant. In the combination of a nonionic surfactant and a cationic surfactant, the mass ratio of the nonionic surfactant to the cationic surfactant may be, for example, 99.5:0.5 to 50:50, or 99:1 to 90:10.

[0203] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkyl alkanolamides, acetylene glycols, oxyethylene adducts of acetylene glycols, polyethylene glycol, polypropylene glycol block copolymers, and the like. Examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, vinyl sulfosuccinates, polyoxyalkylene alkyl ether phosphates, and polyoxyalkylene alkylphenyl ether phosphates. Examples of cationic surfactants include amine salts, amideamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples, though not limited to them, include amine salt-type surfactants such as alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, and quaternary ammonium salt-type surfactants such as benzethonium chloride. Amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, and acetate betaines, specifically long-chain amine oxides, lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.The amount of these surfactants to be used is not particularly limited, but for example, it is preferably 1 to 20% by mass, more preferably 1.5 to 10% by mass, based on the solid content of the emulsion.

[0204] The hydrophilic-lipophilic balance (HLB) of the above emulsifier is not particularly limited. The average HLB of the nonionic emulsifier in the non-fluorine water-repellent agent composition according to one embodiment is preferably 6.0 to 16.0, 6.5 to 15.5, 7.0 to 15.0, or 7.5 to 14.5. If the HLB is outside this range, the initial Bundesmann water repellency and the Bundesmann water repellency after abrasion tend to decrease. The HLB of an emulsifier is a value calculated by the Griffin method, regarding ethyleneoxy groups in the emulsifier as hydrophilic groups.

[0205] (Other Additives) The water-repellent treatment agent may contain an acid, an alkali, a chelating agent, and the like. Further, the water-repellent treatment agent may or may not contain the above isocyanate compound and other crosslinking agents.

[0206] 2.1.3 Content of Non-Fluorine Water-Repellent Component The content of the non-fluorine water-repellent component in the water-repellent treatment agent is not particularly limited. For example, the ratio (mass ratio) of the non-fluorine water-repellent component to the total mass of the water-repellent treatment agent may be 0.1 to 70% by mass, or 0.5 to 50% by mass.

[0207] 2.2 Contact Method In a method for manufacturing a textile product according to one embodiment, the non-fluorine water-repellent component (water-repellent treatment agent containing the non-fluorine water-repellent component) can be applied to the pre-treated textile material by contacting it with the non-fluorine water-repellent component. The method for contacting the textile material with the non-fluorine water-repellent component (water-repellent treatment agent containing the non-fluorine water-repellent component) is not particularly limited. For example, processing methods such as immersion, spraying, and coating can be used. The immersion method may be a continuous method or a batch method. In the continuous method, first, the non-fluorine water-repellent component is diluted in an aqueous solvent to prepare a water-repellent treatment agent (treatment solution). Next, the material to be treated (textile material) is continuously fed into an impregnation device filled with the treatment solution, and after impregnating the material with the treatment solution, the excess treatment solution is removed. The impregnation device is not particularly limited, and padders, kissroll type impregnation devices, gravure coater type impregnation devices, spray type impregnation devices, foam type impregnation devices, coating type impregnation devices, etc., can be preferably used, with padder type being particularly preferred. Next, a dryer is used to remove any remaining solvent from the material to be treated. The dryer is not particularly limited, but a spreader dryer such as a hot flooler or tenter is preferred. The continuous method is preferably used when the material to be treated is a fabric such as a woven cloth. On the other hand, the batch method consists of, for example, a step of immersing the material to be treated in a treatment solution and a step of removing any remaining solvent from the treated material. The batch method is preferably used when the material to be treated is not a fabric, for example, loose hair, top, sliver, hank, tow, yarn, etc., or when the continuous method is unsuitable, such as for knitted fabrics. For the immersion step, for example, a cotton dyeing machine, cheese dyeing machine, jet dyeing machine, industrial washing machine, beam dyeing machine, etc. can be used. For the solvent removal step, a cheese dryer, beam dryer, hot air dryer such as a tumble dryer, high-frequency dryer, etc. can be used.

[0208] 2.3 Heat Treatment After applying the water-repellent component to the fiber material, it is preferable to perform heat treatment as appropriate. There are no particular restrictions on the temperature conditions, but sufficient water repellency can be achieved in the fiber product under mild conditions of 100 to 130°C. High-temperature treatment of 130°C or higher (preferably up to 200°C) is also possible, but in such cases, the treatment time can be shortened compared to when using a fluorine-based water repellent. Therefore, according to the method for manufacturing fiber products of this disclosure, deterioration of the fiber product due to heat is suppressed, the texture of the fiber product becomes flexible during water-repellent treatment, and sufficient water repellency can be imparted to the fiber product under mild heat treatment conditions, i.e., low-temperature curing conditions.

[0209] 2.4 Amount of adhesion After water-repellent treatment, a non-fluorine-based water-repellent component adheres to the fiber material. It is preferable to treat the fiber material with a water-repellent agent in an amount such that the amount of non-fluorine-based water-repellent component adhering is 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass, per 100 parts by mass of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0210] 3. Concomitant use of crosslinking agents In one embodiment of the method for manufacturing a textile product, if particularly to improve durable water repellency, it is preferable to apply a crosslinking agent containing methylolmelamine, isocyanate groups, or a compound having two or more blocked isocyanate groups to the textile material and heat it, in addition to performing pretreatment and water-repellent treatment on the above-mentioned textile material. Furthermore, if it is desirable to further improve durable water repellency, it is preferable that the pretreatment agent or water-repellent treatment agent contains a non-fluorine polymer copolymerized from monomers having functional groups that can react with the above-mentioned crosslinking agent. The compounds having two or more isocyanate groups are as described above. The crosslinking agent may be used alone or in combination of multiple types.

[0211] The crosslinking agent can be applied to the workpiece (textile product) by, for example, dissolving the crosslinking agent in an organic solvent or by immersing the workpiece in a treatment solution in which the crosslinking agent has been emulsified and dispersed in water, and then drying the treatment solution that adheres to the workpiece. By heating the crosslinking agent that has adhered to the workpiece, the reaction between the crosslinking agent, the workpiece, and the non-fluorine water-repellent component can be promoted. To ensure that the reaction of the crosslinking agent proceeds sufficiently and to more effectively improve durable water repellency, it is preferable to heat the workpiece at 110-180°C for 1-5 minutes. The steps of applying the crosslinking agent and heating may be performed simultaneously with the process of treating with the water-repellent agent described above. When performed simultaneously, for example, a second treatment solution containing a non-fluorine water-repellent component and a crosslinking agent is applied to the workpiece, the water is removed, and then the crosslinking agent adhering to the workpiece is further heated. When considering simplification of the water-repellent processing process, reduction of heat, and economic efficiency, it is preferable to perform the process simultaneously with the treatment with the second treatment solution.

[0212] Furthermore, excessive use of the crosslinking agent may impair the texture. It is preferable to use the above crosslinking agent in an amount of 0.01 to 50 parts by mass, or 0.1 to 10 parts by mass, per 100 parts by mass of the material to be treated (textile product).

[0213] 4.Applications Textile products manufactured through the above-described pretreatment and water-repellent treatment possess excellent water repellency (initial water repellency, durable water repellency, Bundesmann water repellency, and water repellency in natural fibers). Furthermore, since these textile products do not use fluorine-based compounds, they can be considered environmentally friendly. Due to their excellent water repellency, these textile products are suitable for a wide range of applications, including clothing and non-clothing items such as down jackets, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, bedding covers, bedding drying covers, curtains, and tents. [Examples]

[0214] As described above, one embodiment of the technology of this disclosure has been explained, but the technology of this disclosure can be modified in various ways other than the above embodiment without departing from its gist. The technology of this disclosure will be described in more detail below with reference to examples, but the technology of this disclosure is not limited to the following examples.

[0215] 1. Preparation of pretreatment agent As a pretreatment agent, a treatment solution containing the following isocyanate compounds was prepared.

[0216] (Preparation example A-1: ​​HDI trimer) As a polyisocyanate, we prepared Duranate TPA-100 (isocyanurate type of hexamethylene diisocyanate, manufactured by Asahi Kasei, NCO group content: 23.1%, NV: 100%).

[0217] (Preparation example A-2: IPDI trimer) In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 150 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate was mixed with propylene glycol diacetate (Dawanol® PGDA, Ando Parachemy Co., Ltd.) as a solvent to completely dissolve the polyisocyanate and obtain a PGDA solution of IPDI trimer. Next, 4.3 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) was mixed into the PGDA solution. To this, 12.8 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac® range, manufactured by Rhodia, EO: 7 mol) was added as an emulsifier, and the mixture was mixed while appropriately cooling it so that the temperature of the mixture was 50°C or lower, to obtain a solution containing 40% by mass of IPDI trimer.

[0218] (Preparation Example A-3: IPDI trimer / HDI trimer nulate) In a reactor similar to that used in Preparation Example A-2, at room temperature, 42 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) was mixed with 98 parts by mass (NCO equivalent: 0.825 mol) of isocyanurate type hexamethylene diisocyanate (HDI) (Duranate TPA-100, manufactured by Asahi Kasei Corporation, NCO group content: 23.1%, NV: 100%) and propylene glycol diacetate (Dawanol® PGDA, Ando Parachemy Co., Ltd.) as a solvent to completely dissolve the polyisocyanate and obtain a PGDA solution of IPDI trimer / HDI trimer. Next, 4.0 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) was mixed into the solution. Then, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac® range, manufactured by Rhodia, EO: 10 mol) was added as an emulsifier, and the mixture was mixed while appropriately cooling it so that the temperature of the mixture was 50°C or lower, to obtain a solution containing 70% by mass of IPDI trimer / HDI trimer nurate.

[0219] (Preparation Example A-4: IPDI trimer / HDI trimer biuret) In the same reactor as that used in Preparation Example A-2, as polyisocyanates, 42 parts by mass (NCO equivalent: 0.62 mol) of isophorone diisocyanate trimer (IPDI trimer) (Vestanat 1890 / 100, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) and 98 parts by mass (NCO equivalent: 0.839 mol) of biuret-type hexamethylene diisocyanate (HDI) (Duranate 24A-100, manufactured by Asahi Kasei Corporation, NCO group content: 23.5%, NV: 100%) were mixed with propylene glycol diacetate as a solvent (Dowanol (registered trademark) PGDA, Ando Parachemi Co., Ltd.) at room temperature, to completely dissolve the polyisocyanates, thereby obtaining a PGDA solution of IPDI trimer / HDI trimer. Then, 4.0 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Inc.) was mixed into the solution. Next, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate as an emulsifier (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 10 mol) was added, and the mixture was mixed while appropriately cooling to keep the temperature of the mixed solution at 50°C or lower, thereby obtaining a solution containing 70% by mass of IPDI trimer / HDI biuret trimer.

[0220] (Preparation Example A-5: Self-emulsifying type of DMP-blocked IPDI / HDI trimer) Trixene Aqua BI-522 (manufactured by Lanxess, solid content: 40%) was diluted with pure water to a solid content of 20%.

[0221] (Preparation Example A-6: DMP-blocked IPDI trimer) In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 150 parts by mass (0.62 mol of NCO equivalent) of Vestat 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate was mixed with 150 parts by mass of diethylene glycol ethyl methyl ether (hereinafter sometimes abbreviated as MEDG) as a solvent at room temperature. 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) was added as a blocking agent in several batches, ensuring that the temperature of the reaction solution did not exceed 50°C, and the mixture was stirred for 1 hour. Subsequently, by measuring the Fourier transform infrared (FT-IR) spectrum, it was confirmed that the peak originating from the NCO group (around 2260 cm-1) disappeared, indicating that blocking had occurred. Next, 21 parts by mass of NIKKOL BC-25 (HLB=18.5, manufactured by Nikko Chemicals Co., Ltd.) was mixed with pure water in small amounts to obtain a dispersion containing 20% ​​by mass of DMP block product of IPDI trimer.

[0222] (Comparative preparation example: Anionic compound) A resin dispersion was prepared containing an anionic compound (dihydroxydiphenylsulfone / formaldehyde condensate, weight-average molecular weight 40,000, manufactured by OG-G Nagase Color Chemical Co., Ltd., SZ9904, solids content 33%) and acetic acid (80% by mass aqueous solution): 0.5 mL / L.

[0223] 2. Preparation of water-repellent treatment agent A treatment solution containing the following non-fluorine-based water-repellent components was prepared as a water-repellent treatment agent.

[0224] 2.1 Preparation of dispersion of acrylic compounds (Preparation example B-1) In an autoclave, 15.6 parts by mass of stearyl acrylate, 0.4 parts by mass of diacetone acrylamide, 0.8 parts by mass of Neugen XL-100 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=14.7), 0.2 parts by mass of stearyltrimethylammonium sulfate, 10 parts by mass of tripropylene glycol, and 68.8 parts by mass of water were placed and mixed and stirred at 45°C to obtain a mixture. This mixture was irradiated with ultrasound to emulsify and disperse all monomers. Next, 0.2 parts by mass of azobis(isobutylamidine) dihydrochloride was added to the dispersion, and under a nitrogen atmosphere, 4.0 parts by mass of vinyl chloride was continuously injected under pressure to maintain an autoclave internal pressure of 0.3 MPa while radical polymerization was carried out at 60°C for 6 hours to obtain a dispersion containing 20% ​​by mass of acrylic resin.

[0225] (Preparation Examples B-2 and B-3) A dispersion containing 20% ​​by mass of acrylic resin was obtained using the same procedure as in Preparation Example B-1, according to the preparation amounts shown in Table 1 below.

[0226] [Table 1]

[0227] 2.2 Preparation of dispersion of silicone-based compounds 2.2.1 Alkyl-modified silicone dispersion (Preparation Example B-4: Octadecyldimethicone dispersion) Methyl hydrogen silicone with a SiH:SiCH3 molar ratio of 5:5 (measured by 1H NMR (nuclear magnetic resonance)) was used as the hydrosilylation catalyst. A mixed solution of platinum(IV) chloride with ethylene glycol monobutyl ether and toluene was added to the flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The flask was purged with nitrogen, and 1 molar equivalent of 1-octadecene was added dropwise to the mixture in the flask for every 1 molar equivalent of the reactive groups (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and the addition reaction was carried out for 6 hours, resulting in the following equation (1): R 20 , R 21 and R 22CH3 is, R 23 C 18 H 37 And a is 40, b is 40, a:b is 1:1, R 30 ~R 35 An alkyl-modified silicone in which CH3 was present was obtained. The completion of the addition reaction was confirmed by FT-IR (Fourier transform infrared) spectroscopy of the obtained alkyl-modified silicone, and by confirming that the absorption spectrum originating from the SiH group of methylhydrogen silicone had disappeared.

[0228] [ka]

[0229] 20 parts by mass of the obtained alkyl-modified silicone, 1.2 parts by mass of SPAN40 (sorbitan-based nonionic surfactant, HLB=6.7), 1.3 parts by mass of TWEEN40 (sorbitan-based nonionic surfactant, HLB=15.6), 0.5 parts by mass of Neugen XL-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=10.5), 0.5 parts by mass of Neugen XL-60 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB=12.5), 0.5 parts by mass of stearyltrimethylammonium sulfate, and 10 parts by mass of dipropylene glycol were mixed while heating. Then, 66.0 parts by mass of water were added to the resulting mixture little by little while mixing to obtain a dispersion containing 20% ​​by mass of octadecyldimethicone (average HLB of nonionic surfactants = 11.4).

[0230] (Preparation Example B-5: Hexacosyldimethicone dispersion) Methyl hydrogen silicone with a SiH:SiCH3 molar ratio of 4:6 (measured by 1H NMR (nuclear magnetic resonance)) was used as the hydrosilylation catalyst. A mixed solution of platinum(IV) chloride with ethylene glycol monobutyl ether and toluene was added to the flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The flask was purged with nitrogen, and 1 molar equivalent of 1-hexacosene was added dropwise to the mixture in the flask for every 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and the addition reaction was carried out for 6 hours, resulting in the formation of R in the above formula (1). 20 , R 21 and R 22 CH3 is, R 23 C 26 H 53 And a is 60, b is 90, a:b is 2:3, R 30 ~R 35 An alkyl-modified silicone in which CH3 was present was obtained. The completion of the addition reaction was confirmed by FT-IR (Fourier transform infrared) spectroscopy of the obtained alkyl-modified silicone, and by confirming that the absorption spectrum originating from the SiH group of methylhydrogen silicone had disappeared.

[0231] Using the obtained alkyl-modified silicone, a dispersion containing 20% ​​by mass of hexacosyldimethicone was obtained in the same manner as in Preparation Example B-4 (average HLB of nonionic surfactant = 9.8).

[0232] (Preparation Example B-6: Dotriacontyldimethicone dispersion) Methyl hydrogen silicone with a SiH:SiCH3 molar ratio of 3:7 (measured by 1H NMR (nuclear magnetic resonance)) was used as the hydrosilylation catalyst. A mixed solution of platinum(IV) chloride with ethylene glycol monobutyl ether and toluene was added to the flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The flask was purged with nitrogen, and 1 molar equivalent of 1-dotriacontene was added dropwise to the mixture in the flask for every 1 molar equivalent of the reactive group (Si-H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and the addition reaction was carried out for 6 hours, resulting in the formation of R in the above formula (1). 20 , R21 , R 22 CH3 is, R 23 C 32 H 65 And a is 140, b is 60, a:b is 7.3, R 30 ~R 35 An alkyl-modified silicone in which CH3 was present was obtained. The completion of the addition reaction was confirmed by FT-IR (Fourier transform infrared) spectroscopy of the obtained alkyl-modified silicone, and by confirming that the absorption spectrum originating from the SiH group of methylhydrogen silicone had disappeared.

[0233] Using the obtained alkyl-modified silicone, a dispersion containing 20% ​​by mass of dotriacontyl dimethicone was obtained in the same manner as in Preparation Example B-4 (average HLB of nonionic surfactant = 8.1).

[0234] Table 2 below summarizes the compositions of adjustment examples B-4 to B-6 and the average HLB of the nonionic surfactants.

[0235] [Table 2]

[0236] 2.2.2 Dispersion of silicone resin, dimethyl silicone, and amino-modified silicone (Preparation example B-7) 5.8 parts by mass of MQ-1600 (trimethylsilyl group-containing polysiloxane, manufactured by Toray Dow Corning Co., Ltd., trade name) as silicone resin and 13.4 parts by mass of KF-96A-100cs (manufactured by Shin-Etsu Silicone Co., Ltd.) as dimethyl silicone were added to a 300 mL stainless steel pot, and the mixture was heated and stirred until the silicone resin was uniformly dissolved. To the resulting homogeneous solution, 0.8 parts by mass of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., amino-modified silicone at both ends, functional group equivalent 2200) was added as amino-modified silicone to obtain a mixture. Next, 1.6 parts by mass of Neugen XL-40 was added, and 78.4 parts by mass of water were added in small increments while mixing. The mixture was then 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 mass of the silicone compound (average HLB of nonionic surfactant = 10.5).

[0237] (Preparation example B-8) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the mixing ratio was as shown in Table 3 below (average HLB of nonionic surfactant = 4.7).

[0238] (Preparation example B-9) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the mixing ratio was as shown in Table 3 below (average HLB of nonionic surfactant = 18.3).

[0239] (Preparation example B-10) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that the mixing ratio was as shown in Table 3 below (average HLB of nonionic surfactant = 10.5).

[0240] 2.2.3 Dispersion of amino-modified silicone (Preparation example B-11) A dispersion containing 20% ​​by mass of a silicone compound was obtained in the same manner as in Preparation Example B-7, except that WACKER FINISH WR 301 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., amine equivalent 3700, solids content 100%) was used as the amino-modified silicone, and the blending ratio was as shown in Table 3 below (average HLB of nonionic surfactant = 12.0).

[0241] 2.2.4 Dispersion of silicone resin (Preparation example B-12) A dispersion containing 20% ​​by mass of silicone resin was obtained in the same manner as in Preparation Example A-7, except that IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.) was used as the solvent and the blending ratio was as shown in Table 3 below (average HLB of nonionic surfactant = 4.7).

[0242] [Table 3] Regarding nonionic surfactants, we have SPAN65: HLB 2.1 (manufactured by Croda), Neugen XL-160: HLB 16.3 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and NIKKOL BC-30: HLB 19.5 (manufactured by Nikko Chemicals Co., Ltd.). Neugen XL-40 is as described above.

[0243] 2.3 Preparation of dispersion of wax-based compounds (Preparation example B-13) 20 parts by mass of Paraffin Wax-155 (manufactured by Nippon Seiro Co., Ltd., melting point 69°C), 78 parts by mass of water, 1.0 part by mass of sorbitan monostearate (HLB=4.5), and 1.0 part by mass of polyoxyethylene sorbitan monostearate (HLB=14.9) were placed in a high-pressure reaction vessel and sealed. The contents of the vessel were then heated to 110-120°C while stirring. Subsequently, the contents of the vessel were emulsified under high pressure for 30 minutes to obtain an emulsion containing 20% ​​by mass of paraffin wax (average HLB=9.7 of nonionic surfactants).

[0244] 2.4 Preparation of dispersion of urethane compounds 2.4.1 Synthesis of polyurethane resin (Synthesis example U-1) In a reactor equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser, under a nitrogen atmosphere, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, trade name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol antioxidant), and 0.25 parts by mass of tetraphenyl-dipropylene glycol diphosphite (organic phosphite ester, co-catalyst) were mixed. Then, 10.7 parts by mass of 1,3-butanediol was added to this mixture, and nitrogen was introduced into the liquid phase for 1 hour. Subsequently, the mixture was heated to 80°C and reacted for 3 hours, after which it was cooled to 60°C. Then, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium·2-ethylhexanoate was added as an isocyanuration catalyst, and the reaction was carried out for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added to 100 parts by mass of HDI. This reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum 93.3 Pa) and distilled until the remaining HDI monomer content was 0.5% or less, 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 count of 3.0.

[0245] 2.4.2 Preparation of polyurethane resin dispersion (Preparation example B-14) In a reactor equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube, 100.08 parts by mass of the aliphatic polyisocyanate derivative of Synthesis Example U-1 and 90.03 parts by mass of Calcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound were mixed and reacted at 110°C under a nitrogen atmosphere for 4 hours until the concentration of isocyanate groups reached 3.67%. Next, the reaction mixture was cooled to 80°C, and 9.89 parts by mass of N-methyldiethanolamine as a cationic active hydrogen compound was added and reacted at 80°C for 1 hour. 50 parts by mass of methyl ethyl ketone was added as a solvent and reacted at 80°C until the disappearance of isocyanate groups could be confirmed by infrared absorption spectroscopy. Next, 57.7 parts by mass of methyl ethyl ketone (MEK) was added to the reaction mixture, the temperature was raised to 80°C, and after mixing until the reaction mixture was completely dissolved, it was cooled to 75°C. Subsequently, 18.93 parts by mass of acetic acid was added as an acid compound to neutralize the mixture. Next, while maintaining the reaction solution at 75°C, 20 parts by mass of NIKKOL Hexaglyn 1-SV (HLB=9.0, manufactured by Nikko Chemicals Co., Ltd.) was added and mixed, and 800 parts by mass of ion-exchanged water heated to 70°C was gradually added to emulsify the mixture. Then, MEK was removed by distillation using an evaporator under reduced pressure at a water bath temperature of 60°C. Finally, a dispersion containing polyurethane resin was obtained by adjusting the solid content concentration with ion-exchanged water to 20% by mass (average HLB of nonionic surfactant = 9.0, solid content 20% by mass).

[0246] 2.5 Preparation of dispersion of dendrimer compounds (Preparation example B-15) In a four-necked round-bottom flask equipped with an overhead stirrer, thermocouple, and Dean-Stark / condenser, 15.3 parts by mass of sorbitan tristearate (hydroxyl value = 77.2 mg KOH / g) and 24.7 parts by mass of 4-methyl-2-pentanone (MIBK) were added. The solution was refluxed for 1 hour to remove residual moisture. After 1 hour, the solution was cooled to 50°C, and 4.0 parts by mass of DESMODUR N-100, followed by the catalyst, were added. The solution was heated to 80°C for over 1 hour to obtain a dendrimer solution.

[0247] 52.7 parts by mass of water, 0.7 parts by mass of ARMEEN DM-18D, 2.0 parts by mass of TERGITOL TMN-10, and 0.6 parts by mass of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was then heated to 60°C. The dendrimer solution prepared above was cooled to 60°C, and the heated surfactant solution was slowly added to prepare a 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% ​​dendrimer compounds (average HLB of nonionic surfactant = 14.4, solids content 20% by mass).

[0248] 3. Treatment of fibers The water-repellent properties of treated fabrics were evaluated using two methods: a single-step bath treatment using a treatment solution containing an isocyanate compound and a water-repellent component, and a two-step bath treatment using a treatment solution containing one of these two components and a treatment solution containing the other component. The treated fabrics used were polyester (PET) woven fabric, nylon (Ny) woven fabric, cotton woven fabric, and a woven fabric consisting of polyester / cotton = 50% / 50% (T / C).

[0249] 3.1 Separate bath treatment (Examples 1-22, Comparative Example 1) A first treatment solution was prepared by diluting an isocyanate compound dispersion with water to achieve the composition (mass%) shown in Table 4 or 5 below, and the treated fabric was immersed in this first treatment solution for pretreatment. After pretreatment, the fabric was dried at 130°C for 1 minute to obtain the treated fabric (first treated fabric) treated with the first treatment solution. Subsequently, a second treatment solution was prepared by diluting a water-repellent component dispersion with water to achieve the composition shown in Table 4 or 5, and the first treated fabric was immersed in this second treatment solution for water-repellent treatment. After water-repellent treatment, the fabric was dried at 100°C or 170°C for 1 minute to obtain a water-repellent textile product.

[0250] 3.2 Same bath treatment (Comparative Examples 2, 3, and 5) A treatment solution for the bath treatment was prepared by mixing an isocyanate compound dispersion and a water-repellent component dispersion, and then diluting it with water to the composition (mass%) shown in Table 4 or 5 below. The water-repellent treatment was performed by immersing the treated cloth in this treatment solution. After the water-repellent treatment, the cloth was dried at 100°C or 170°C for 1 minute to obtain a water-repellent textile product.

[0251] 3.3 Water-repellent treatment only (Comparative Example 4) The treated fabric was subjected to a water-repellent treatment without any prior treatment. Specifically, a treatment solution was prepared by diluting a water-repellent component dispersion with water to the composition (mass%) shown in Table 4 below. The treated fabric was immersed in this treatment solution to perform the water-repellent treatment. After the water-repellent treatment, it was dried at 170°C for 1 minute to obtain a water-repellent textile product.

[0252] 4. Evaluation Method 4.1 Evaluation of initial water repellency of textile products The water repellency of the above textile products was evaluated by testing them in accordance with the spray method of JIS L1092 (2009) with a shower water temperature of 20°C. The results were evaluated visually using the following grades. A "+" was added to the grade if the properties were slightly better, and a "-" was added if the properties were slightly worse. Water repellency: condition 5: Items that are not wet or adhering to the surface. 4: Those showing slight adhesion and moisture on the surface. 3: Those showing partial wetting on the surface. 2: Those showing moisture on the surface 1: Those showing moisture across the entire surface. 0: Both sides are completely wet.

[0253] 4.2 Evaluation of Durable Water Repellency of Textile Products The above textile products were washed 20 times (L-20) or 100 times (L-100) according to method 103 of JIS L0217 (1995), and the water repellency after air drying was evaluated using the same procedure and grade as above.

[0254] 4.3 Evaluation of water repellency of textile products after abrasion 4.3.1 Preparation of abrasion cloth According to the Martindale method of JIS L1096:2010 Method E, a test piece made of the above textile product was attached to the sample holder of a Martindale abrasion tester, a standard friction cloth was attached to the friction table of the abrasion tester, the sample holder was placed on top of the standard friction cloth, a pressing load of 9 kPa was applied, and the cloth was rubbed 1000 times to obtain an abrasion cloth for evaluation.

[0255] 4.3.2 Evaluation of initial and durable water repellency of abrasion fabrics The water repellency of the above-mentioned abrasion cloth was evaluated using the same procedure and grading system as described above.

[0256] 4.4 Bundesmann rainfall test For each of the textile products described above—before abrasion (before washing), after washing, and after abrasion—water repellency, water absorption, and water absorption rate were evaluated after a rainfall test conducted according to the method described in JIS L1092:2009 7.3 Rain test (shower test) Method A. The rainfall duration was set to 10 minutes. Water repellency was graded from 1 to 5 according to the wet state shown in Figure 1. A higher score indicates better repellency. A + (-) next to the grade indicates that the respective property is slightly better (worse).

[0257] 5. Evaluation Results The evaluation results are shown in Tables 4 and 5 below.

[0258] [Table 4]

[0259] [Table 5]

[0260] The results shown in Tables 4 and 5 indicate the following: (1) When the fiber material is pretreated with an isocyanate compound and then treated with a non-fluorine-based water-repellent component in a separate bath (Examples 1-21), the water-repellent properties of the textile product during washing, the Bundesmann rain test, and the water repellency of natural fibers are improved compared to when the water-repellent treatment is performed in the same bath (Comparative Examples 2 and 3). (2) The effect of the separate bath treatment described above is better when an unblocked isocyanate is used as the isocyanate compound during pretreatment (Example 2) than when a blocked isocyanate is used (Example 6). (3) When low-temperature drying is performed after water-repellent treatment, a comparison is made between a separate bath treatment (Example 22) and the same bath treatment (Comparative Example 5), and the separate bath treatment ensures sufficient wash-durable water-repellent performance.

[0261] Based on the above results, it can be said that a textile product manufacturing method, which includes contacting a fiber material with an isocyanate compound and then contacting the fiber material with a non-fluorine-based water-repellent component after contact with the isocyanate compound, can produce a textile product with excellent water repellency.

[0262] In the above examples, an example was given of imparting water repellency to textile products using an isocyanate group-containing compound and a non-fluorine-based water-repellent composition, but the technology of this disclosure is not limited to this form. The processing method of this disclosure is thought to be able to impart excellent initial water repellency and durable water repellency to various articles other than textile products. In particular, as shown in the above examples, it is suitable for imparting durable water repellency, Bundesmann water repellency, and water repellency in natural fibers to textile products.

Claims

1. Contacting the fibrous material with an isocyanate compound, and After contacting the fiber material with the isocyanate compound, a non-fluorine water-repellent component is brought into contact with the fiber material. Includes, The isocyanate compound is a polyisocyanate polymer. A method for manufacturing textile products.

2. The isocyanate compound is at least one of aliphatic isocyanates, aromatic isocyanates, aromatic aliphatic isocyanates, and alicyclic isocyanates. A method for manufacturing a textile product according to claim 1.

3. The isocyanate compound is a non-blocked isocyanate. A method for manufacturing a textile product according to claim 1 or 2.

4. The non-fluorinated water-repellent component is at least one of acrylic compounds, silicone compounds, wax compounds, urethane compounds, and dendrimer compounds. A method for manufacturing a textile product according to claim 1 or 2.

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