Method for producing fibrous product

Abstract

Provided is a method for producing a fibrous product demonstrating excellent water repellency. 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.

Description

Textile manufacturing method

[0001] The present application discloses a method for manufacturing a textile product.

[0002] Fluorine-based water repellents containing fluorine-containing groups are known. Treating textiles and other articles with a fluorine-based water repellent can impart excellent water repellency to the article. Fluorine-based water repellents are generally produced by polymerizing or copolymerizing a monomer having a fluoroalkyl group. To achieve sufficient water repellency, the fluoroalkyl groups must be oriented properly. Typically, the article is subjected to a heat treatment at a temperature exceeding 130°C after the fluorine-based water repellent has been attached to the article. However, such heat treatment is undesirable from the viewpoint of energy conservation. Furthermore, fluoroalkyl group-containing monomers are not only expensive but also persistent, resulting in a significant environmental impact. Given these circumstances, techniques have been developed in recent years to impart excellent water repellency to textiles and other articles by treating the articles with non-fluorine-based water repellents that do not contain fluorine. For example, Patent Documents 1 to 3 disclose techniques in which a non-fluorine-based water repellent is contacted with fibers pretreated with an anionic compound.

[0003] JP 2017-210704 A JP 2019-026965 A International Publication No. 2015 / 083627 A

[0004] Conventional techniques using non-fluorinated water repellents still have room for improvement. For example, the water repellency under severe conditions, such as the washing durable water repellency of natural fibers and the Bundesmann rainfall test of synthetic fibers, may not be sufficient. In this regard, a new technique is needed that can impart excellent water repellency to textile products (for example, the washing durable water repellency of natural fibers and the water repellency after the Bundesmann rainfall test (Bundesmann water repellency) of synthetic fibers).

[0005] The present application discloses the following multiple aspects as means for solving the above-mentioned problems. <Aspect 1> A method for producing a textile product, comprising: bringing an isocyanate compound into contact with a textile material; and bringing a non-fluorinated water-repellent component into contact with the textile material after contact with the isocyanate compound. <Aspect 2> A method for producing a textile product according to Aspect 1, in which the isocyanate compound is a polyisocyanate. <Aspect 3> A method for producing a textile product according to Aspect 1 or 2, in which the isocyanate compound is at least one of an aliphatic isocyanate, an aromatic isocyanate, an aromatic-aliphatic isocyanate, and an alicyclic isocyanate. <Aspect 4> A method for producing a textile product according to any of Aspects 1 to 3, in which the isocyanate compound is an unblocked isocyanate. <Aspect 5> A method for producing a textile product according to any of Aspects 1 to 4, in which the non-fluorinated water-repellent component is at least one of an acrylic compound, a silicone compound, a wax compound, a urethane compound, and a dendrimer compound.

[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, a fiber product having excellent initial water repellency, durable water repellency, and Bundesmann water repellency can be produced.

[0007] The evaluation criteria for the Bundesmann Rainfall Test are shown.

[0008] Hereinafter, a method for manufacturing a textile product according to one embodiment will be described, but the method for manufacturing a textile product according to the present disclosure is not limited to this embodiment.

[0009] A method for producing a textile product according to one embodiment includes contacting a textile material with an isocyanate compound and contacting the fibers, after contacting the fibers with the isocyanate compound, with a non-fluorine-based water-repellent component. In other words, the method for producing a textile product according to one embodiment includes pretreating the textile material with the isocyanate compound and then performing a water-repellent treatment with the non-fluorine-based water-repellent component.

[0010] 1. Pretreatment In one embodiment of the method for producing a textile product, the pretreatment involves bringing a textile material into contact with an isocyanate compound.

[0011] 1.1 Fiber Material The type of fiber material is not particularly limited. The fiber material may be at least one selected from natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (e.g., nylon), polyester, polyurethane, and polypropylene; and composite fibers, blended fibers, and the like thereof. The fiber material may be in any form, such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, and paper. In one embodiment of the water-repellent fiber product, the fiber material preferably contains polyamide and polyester as raw materials, from the viewpoint of achieving superior water repellency. In particular, the fiber material is preferably at least one selected from nylons such as nylon 6 and nylon 6,6; polyesters such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid; and blended fibers containing these.

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

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

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

[0015] The polyisocyanate monomer is not particularly limited, and examples thereof include aliphatic polyisocyanates, aromatic polyisocyanates, aromatic aliphatic polyisocyanates, alicyclic polyisocyanates, etc. These polyisocyanate monomers can be used alone or in combination of two or more.

[0016] The polyisocyanate derivative is not particularly limited, and examples thereof include multimers of polyisocyanate monomers (for example, dimers, trimers (for example, isocyanurate-modified products, iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (for example, allophanate-modified products produced by further adding an isocyanate group of a polyisocyanate monomer to a urethane group formed by the reaction of the above-mentioned polyisocyanate monomer with a low-molecular-weight polyol described below), adducts (for example, adducts (alcohol adducts) produced by the reaction of a polyisocyanate monomer with a low-molecular-weight polyol described below), and biuret-modified products (for example, Examples of suitable polyisocyanate derivatives include biuret-modified products produced by reacting the polyisocyanate monomers with water or amines, urea-modified products (e.g., urea-modified products produced by adding an isocyanate group of a polyisocyanate monomer to a urea group formed by the reaction of the polyisocyanate monomers with a diamine), oxadiazinetrione-modified products (e.g., oxadiazinetrione produced by reacting the polyisocyanate monomers with carbon dioxide), carbodiimide-modified products (e.g., carbodiimide-modified products produced by the decarboxylation condensation reaction of the polyisocyanate monomers), uretdione-modified products, and uretonimine-modified products. Further examples of polyisocyanate derivatives include polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). These polyisocyanate derivatives can be used alone or in combination of two or more.

[0017] From the viewpoint of Bundesmann water repellency, the polyisocyanate is preferably a polymer of the above-mentioned monomers. In particular, when the polyisocyanate is a trimer, Bundesmann water repellency is more likely to be improved.

[0018] As described above, the polyisocyanate may be used alone or in combination of two or more. The polyisocyanate may also be a reaction product of two or more isocyanate compounds. When two or more polyisocyanates are used in combination, a combination of an aliphatic and an alicyclic polyisocyanate is preferred. In this case, the mass ratio of the aliphatic polyisocyanate to the alicyclic polyisocyanate may preferably be 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 the aliphatic polyisocyanate and the alicyclic polyisocyanate are contained in this ratio, the durable water repellency of the Bundesmann is even better.

[0019] (Aliphatic Isocyanate) 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-diisocyanatomethyl caproate, lysine diisocyanate, dimer acid diisocyanate, etc. From the viewpoint of excellent washing durability and water repellency in natural fibers, 1,6-hexamethylene diisocyanate (HDI) is preferred as the aliphatic isocyanate.

[0020] (Aromatic Isocyanate) 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, and the like.

[0021] (Aromatic Aliphatic Isocyanate) 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'-diisocyanato-1,4-diethylbenzene, and the like.

[0022] (Alicyclic Isocyanate) Examples of alicyclic isocyanates include 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), and trans, trans-

[0049] The isomer may be at least one selected from the group consisting of methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H6XDI, hydrogenated XDI), and the like. From the viewpoint of excellent Bundesmann and 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 Isocyanate / Unblocked Isocyanate) The isocyanate compound may be blocked with a blocking agent, or may be unblocked. In particular, from the viewpoint of durable water repellency, the isocyanate compound is preferably an unblocked isocyanate (unblocked isocyanate). The blocked isocyanate 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.

[0024] The blocking agent may be, for example, a compound having one or more active hydrogen atoms in the molecule, and 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. Among these, at least one selected from acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds is preferred, and 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. Among these, from the viewpoint of durable water repellency after washing, one or both of dimethylpyrazole and malonic acid diester are more preferred.

[0025] (Self-emulsifying property) The above-mentioned isocyanate compound may or may not have self-emulsifying property.As the isocyanate compound having self-emulsifying property, for example, polyisocyanate in which nonionic hydrophilic group, cationic hydrophilic group, or anionic hydrophilic group is introduced into a part of polyisocyanate can be mentioned.From the viewpoint of water repellency, preferably polyisocyanate in which nonionic hydrophilic group having oxyethylene group is introduced can be used. Examples of hydrophilic compounds that can be 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; (poly)ethylene glycols such as ethylene glycol, 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 random copolymers and block copolymers of ethylene oxide and butylene oxide; polyoxyalkylene monoamines; polyoxyalkylenediamines; and the like, among which polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether are preferably used. The above-mentioned nonionic hydrophilic compounds may be used alone or in combination of two or more. By introducing these compounds in 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 Components The pretreatment agent may contain other components such as a solvent and an emulsifier in addition to the isocyanate compound.

[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 solvents, ketone solvents, hydrocarbon solvents, aromatic solvents, ester solvents, and nitrogen-containing solvents. The amount of the solvent may be 0.1 to 70% by mass, 5 to 50% by mass, or 10 to 30% by mass, with the entire pretreatment agent being 100% by mass.

[0028] (Emulsifier) ​​The pretreatment agent may contain an emulsifier to improve the dispersibility of the isocyanate compound and the like in the solvent. The emulsifier may be at least one selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. In the case of a blocked isocyanate, the emulsifier is preferably a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant from the viewpoint of water repellency. 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 an unblocked isocyanate, an anionic surfactant is most preferred from the viewpoint of protecting the isocyanate group.

[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, alkylalkanolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, etc. Examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylate salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, vinyl sulfosuccinate, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ether phosphates, etc. Examples of cationic surfactants include amine salts, amidoamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples include, but are not limited to, amine salt surfactants such as alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Examples of amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amidobetaines, and acetic acid betaine, and specific examples include long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.The amount of these surfactants used is not particularly limited, but is preferably 1 to 20% by mass, more preferably 1.5 to 10% by mass, of the solid content of the emulsion.

[0030] The hydrophilic-lipophilic balance (HLB) of the emulsifier is not particularly limited. The average HLB of the nonionic emulsifier in the pretreatment agent 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 the emulsifier is determined by the following formula using the Griffin method, regarding the ethyleneoxy group in the surfactant as the hydrophilic group: HLB = 20 × [(molecular weight of the hydrophilic group contained in the surfactant) / (molecular weight of the surfactant)]

[0031] (Other Additives) The pretreatment agent may contain an acid, an alkali, a chelating agent, or the like.

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

[0033] 1.3 Contact Method In one embodiment of the method for producing a textile product, the isocyanate compound (pretreatment agent containing an isocyanate compound) is brought into contact with the textile material, thereby adhering the isocyanate compound to the textile material. The method for contacting the textile material with the isocyanate compound (pretreatment agent containing an isocyanate compound) is not particularly limited. Examples of processing methods include immersion, spraying, and coating. The immersion method may be a continuous method or a batch method. In a continuous method, the isocyanate compound is first diluted in a solvent to prepare a pretreatment agent (treatment liquid). Next, the workpiece (textile material) is continuously fed into an impregnation device filled with the treatment liquid, and the workpiece is impregnated with the treatment liquid. After that, unnecessary treatment liquid is removed. The impregnation device is not particularly limited, and a padder, a kiss-roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator, etc. can be preferably used, with the padder type being particularly preferred. Subsequently, the solvent remaining in the treated material is removed using a dryer. The dryer is not particularly limited, and preferred are open-air dryers such as hot flue dryers and tenter dryers. The continuous method is preferably used when the treated material is in the form of a fabric, such as a woven fabric. On the other hand, the batch method comprises, for example, a step of immersing the treated material in a treatment solution and a step of removing the solvent remaining in the treated material. The batch method is preferably used when the treated material is not in the form of a fabric, such as loose fibers, tops, slivers, hanks, tows, or yarns, or when the treated material is not suitable for a continuous method, such as knitted fabrics. For the immersion step, for example, a cotton dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, or the like can be used. For the solvent removal operation, a cheese dryer, a beam dryer, a hot air dryer such as a tumble dryer, a high-frequency dryer, or the like can be used.

[0034] 1.4 Drying After contacting the fibrous material with the pretreatment agent (treatment liquid), it is preferable to dry it thoroughly. The temperature for the dry heat treatment is preferably 100 to 200°C, and particularly preferably 120 to 180°C. The time for the dry heat treatment is preferably 10 seconds to 3 minutes, and particularly preferably 1 to 2 minutes. The method for dry heat treatment is not particularly limited, but a tenter is preferable when the material to be treated is in the form of a fabric.

[0035] 1.5 Amount of Deposition An isocyanate compound is deposited on the textile material after pretreatment. The pretreatment agent is preferably used in an amount such that the amount of the isocyanate compound deposited is 0.01 to 3 parts by mass, or 0.1 to 1 part by mass, per 100 parts by mass of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0036] 2. Water-repellent Treatment In one embodiment of the method for producing a textile product, the textile material after the pretreatment (after contact with the isocyanate compound) is contacted with a non-fluorine-based water-repellent component. For example, a water-repellent treatment agent containing a non-fluorine-based water-repellent component is prepared, and the water-repellent treatment agent is contacted with the textile material.

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

[0038] 2.1.1 Non-fluorine-based water-repellent component The non-fluorine-based water-repellent component may be, for example, at least one of an acrylic compound, a silicone compound, a wax compound, and a dendrimer compound. From the viewpoints of durable water repellency and Bundesmann water repellency, the non-fluorine-based water-repellent component is preferably one or both of an acrylic compound and a silicone compound, and more preferably a silicone compound.

[0039] (Acrylic Compound) The acrylic compound has, for example, a structural unit derived from a (meth)acrylic acid ester monomer (hereinafter also referred to as "component (A1)") represented by the following general formula (A1). The acrylic compound may further have a structural unit derived from a compound (hereinafter also referred to as "component (A2)") represented by the following general formula (A2). In the present 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] [In formula (A1), R １ is hydrogen or a methyl group, and R ２ represents a monovalent hydrocarbon group having 12 to 30 carbon atoms which may have a substituent.]

[0041] [In formula (A2), R １１ is hydrogen or a methyl group, and R １２ is a divalent hydrocarbon group having 1 to 6 carbon atoms, Z is an ester group or an amide group, and W is —CO—R １３ (R １３ is a monovalent hydrocarbon group having 1 to 4 carbon atoms), a group represented by —NH—CO—NH ２ or a group represented by the following formula (W1):

[0042]

[0043] The component (A1) has a monovalent hydrocarbon group having 12 to 30 carbon atoms, which may have a substituent. This hydrocarbon group may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic or aromatic ring structure. Among these, from the viewpoint of water repellency, linear groups are preferred, and linear alkyl groups are more preferred. In this case, the water repellency is even better. When the monovalent hydrocarbon group having 12 to 30 carbon atoms has a substituent, examples of the substituent include one or more of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, a blocked isocyanate group, and a (meth)acryloyloxy group. In the general formula (A-1) above, R ２ is preferably an unsubstituted hydrocarbon group.

[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. A particularly preferred hydrocarbon group is a linear alkyl group having 18 to 22 carbon atoms.

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

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

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

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

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

[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 —NH—CO—NH ２ or a group represented by the above formula (W1). When Z is an amide group, R １２ is preferably a hydrocarbon group having 2 to 4 carbon atoms, and W is —CO—R １３ Preferably, R is a group represented by １３ It is preferable that the number of carbon atoms is 1 to 2.

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

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

[0053] Regarding the content ratio of the structural units derived from component (A1) and the structural units derived from component (A2) in the acrylic compound, the ratio (A1) / (A2) of the mass of the blended component (A1) to the mass of the blended component (A2) is preferably 100 / 0 to 70 / 30, more preferably 99.9 / 0.1 to 70 / 30, even more preferably 99.8 / 0.2 to 80 / 20, and particularly preferably 99.7 / 0.3 to 90 / 10. When (A1) / (A2) is within the above range, durable water repellency and water repellency are improved.

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

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

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

[0057] The mass of the (A3) component to be blended is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, relative to the total mass of the (A1) component and the (A2) component, 100 parts by mass, from the viewpoints of water repellency, durable water repellency, and peel strength. The mass of the (A3) component to be blended 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 the (A1) component and the (A2) component, 100 parts by mass, from the viewpoints of water repellency, durable water repellency, and texture.

[0058] In terms of improving emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization, the acrylic compound preferably contains, in addition to component (A1) and any component (A2), at least one reactive emulsifier (A4) (hereinafter also referred to as "component (A4)") as a monomer component selected from compounds having an HLB of 7 to 18 and represented by the following general formula (A4-1), compounds having an HLB of 7 to 18 and represented by the following general formula (A4-2), and compounds (A4-3) in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil or fat having an HLB of 7 to 18 and having a hydroxyl group and a polymerizable unsaturated group.

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

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

[0061] In the present application, the term "reactive emulsifier" refers to an emulsifying dispersant having radical reactivity, i.e., a surfactant having one or more polymerizable unsaturated groups in the molecule, which can be copolymerized with a monomer such as a (meth)acrylic acid ester.

[0062] "HLB" refers to the HLB value calculated by the Griffin method, regarding the ethyleneoxy group in the reactive emulsifier as a hydrophilic group.

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

[0064] In the above general formula (A4-1), R ３ is hydrogen or a 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 emulsion stability of the acrylic compound. Y １ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. １ The type, combination and number of alkyleneoxy groups in may be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure.

[0065] The compound represented by the above general formula (A4-1) is preferably a compound represented by the following general formula (A4-1-1).

[0066] [In formula (A4-1-1), R ３ is hydrogen or a methyl group, X is a linear or branched alkylene group having 1 to 6 carbon atoms, and A １ O is an alkyleneoxy group having 2 to 4 carbon atoms, and m can be appropriately selected so as to fall within the above HLB range. Specifically, an integer of 1 to 80 is preferred. When m is 2 or more, m A １ O may be the same or different.

[0067] In the compound represented by the general formula (A4-1-1), R ３ is hydrogen or a 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 emulsion stability of the acrylic compound. A １ O is an alkyleneoxy group having 2 to 4 carbon atoms. １The types and combinations of O and the number m can be appropriately selected so as to fall within the above HLB range. From the viewpoint of emulsion stability of the acrylic compound, m is preferably an integer of 1 to 80, more preferably an integer of 1 to 60. When m is 2 or more, m A １ O may be the same or different. １ When there are two or more types of O, they may have a block addition structure or a random addition structure.

[0068] The reactive emulsifier represented by the general formula (A4-1-1) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained as a commercially available product, such as "Latemul PD-420," "Latemul PD-430," and "Latemul PD-450" manufactured by Kao Corporation.

[0069] In the above general formula (A4-2), R ４ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group. Examples of the unsaturated hydrocarbon group include a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, and a heptadecatrienyl group. In terms of emulsion stability of acrylic compounds, R ４ is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.

[0070] Y ２ is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms. ２ The type, combination, and number of alkyleneoxy groups in the above formula (1) can be appropriately selected so as to fall within the above HLB range. When two or more types of alkyleneoxy groups are used, they may have a block addition structure or a random addition structure. In terms of emulsion stability of the acrylic compound, the alkyleneoxy group is preferably an ethyleneoxy group.

[0071] The compound represented by the above general formula (A4-2) is preferably a compound represented by the following general formula (A4-2-1).

[0072] [In formula (A4-2-1), R ４ is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group, and A ２ O is an alkyleneoxy group having 2 to 4 carbon atoms, and n can be appropriately selected so as to fall within the above-mentioned HLB range. Specifically, an integer of 1 to 50 is preferred. When n is 2 or more, n A ２ O may be the same or different.

[0073] R in the compound represented by the above general formula (A4-2-1) ４ represents R in the above general formula (A4-2). ４ The same can be mentioned.

[0074] A ２ O is an alkyleneoxy group having 2 to 4 carbon atoms. In terms of emulsion stability of acrylic compounds, A ２ The types and combinations of O and the number of n can be appropriately selected so as to fall within the above HLB range. ２ O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14. When n is 2 or more, n A ２ O may be the same or different. ２ When there are two or more types of O, they may have a block addition structure or a random addition structure.

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

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

[0077] Compound (A4-3) has an HLB of 7 to 18 and is obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a fat or oil having a hydroxyl group and a polymerizable unsaturated group. Examples of the fat or oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids containing at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoleidic acid, 2-hydroxytetracosenoic acid, etc.). From the viewpoint of emulsion stability of acrylic compounds, alkylene oxide adducts of triglycerides of fatty acids containing at least one hydroxy unsaturated fatty acid are preferred, alkylene oxide adducts of castor oil (triglycerides of fatty acids containing ricinoleic acid) having 2 to 4 carbon atoms are more preferred, and ethylene oxide adducts of castor oil are even more preferred. Furthermore, the number of moles of alkylene oxide added can be appropriately selected so as to fall within the above-mentioned HLB range, and from the viewpoint of emulsion stability of acrylic compounds, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. Furthermore, when two or more types of alkylene oxides are used, they can have a block addition structure or a random addition structure.

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

[0079] The constituent ratio of the monomer of the component (A4) in the acrylic compound is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and even more preferably 3 to 10 mass%, relative to the total amount of monomer components constituting the acrylic compound, from the viewpoint of improving water repellency and emulsion stability in the composition during and after emulsion polymerization or dispersion polymerization of the acrylic compound.

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

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

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

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

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

[0085] The monomer (A5-1) is a (meth)acrylic acid ester monomer having a monovalent chain hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester moiety. In terms of reactivity with a crosslinking agent, the monovalent chain hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. When a textile product is treated with an acrylic compound containing the monomer (A5-1) having a group reactive with such a crosslinking agent, together with the crosslinking agent, the durable water repellency of the resulting textile product can be improved while maintaining its texture. The isocyanate group may be a blocked isocyanate group protected with a blocking agent.

[0086] The chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The chain hydrocarbon group may further have a substituent in addition to the functional group. Among these, a linear and / or saturated hydrocarbon group is preferred in terms of improving durable water repellency.

[0087] Specific examples of the monomer (A5-1) include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving durable water repellency. Dimethylaminoethyl (meth)acrylate is also preferred in terms of improving texture.

[0088] From the viewpoint of water repellency, the mass of the blended component (A5-1) is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, relative to 100 parts by mass of the combined mass of the blended components (A1) and (A2). From the viewpoint of water repellency, the mass of the blended component (A5-1) is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the combined mass of the blended components (A1) and (A2).

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

[0090] From the viewpoint of water repellency, the mass of the blended component (A5-2) is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the blended components (A1) and (A2). From the viewpoint of water repellency, the mass of the blended component (A5-2) is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the blended components (A1) and (A2).

[0091] The monomer (A5-3) is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester moiety. The chain hydrocarbon group having 1 to 4 carbon atoms is preferably a linear hydrocarbon group having 1 to 2 carbon atoms or a branched hydrocarbon group having 3 to 4 carbon atoms. Examples of the chain hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Specific examples of the compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred, in terms of improving durable water repellency.

[0092] From the viewpoint of water repellency, the mass of the blended component (A5-3) is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the blended components (A1) and (A2). From the viewpoint of water repellency, the mass of the blended component (A5-3) is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the blended components (A1) and (A2).

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

[0094] From the viewpoint of water repellency, the mass of the blended component (A5-4) is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the blended components (A1) and (A2). From the viewpoint of water repellency, the mass of the blended component (A5-4) is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the blended components (A1) and (A2).

[0095] From the viewpoints of water repellency and texture, the total constituent ratio of the monomers of the component (A5) in the acrylic compound is preferably 1 to 30 mass %, more preferably 3 to 25 mass %, and even more preferably 5 to 20 mass %, relative to the total amount of the monomer components constituting the acrylic compound.

[0096] From the viewpoint of water repellency, the mass of the (A5) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the combined mass of the (A1) component and the (A2) component to be blended. From the viewpoint of water repellency, the mass of the (A5) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the combined mass of the (A1) component and the (A2) component to be blended.

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

[0098] Examples of component (A6) include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group other than the above (A1), (A2), and (A5), (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylolacrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other fluorine-free vinyl monomers other than component (A3). Note that (meth)acrylic acid esters having a hydrocarbon group other than components (A1), (A2), and (A5) may have a substituent on the hydrocarbon group such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group, or may have a substituent other than a group reactive with a crosslinking agent such as a quaternary ammonium group, and may have an ether bond, ester bond, amide bond, urethane bond, or the like. Examples of (meth)acrylic acid esters other than components (A1), (A2), and (A5) include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, etc. Among these, (meth)acryloylmorpholine is more preferred in that it can improve the peel strength of the resulting textile product against coatings.

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

[0100] The acrylic compound preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group that can react with a crosslinking agent, in order to improve durable water repellency. The isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. The acrylic compound preferably has an amino group in order to improve texture.

[0101] The weight-average molecular weight of the acrylic compound is preferably 30,000 or more. When the weight-average molecular weight is 30,000 or more, water repellency tends to be further improved. Furthermore, the weight-average molecular weight of the acrylic compound is more preferably 50,000 or more. In this case, water repellency can be more fully exhibited. The upper limit of the weight-average molecular weight of the acrylic compound is preferably about 5,000,000.

[0102] The weight-average molecular weight of the acrylic compound is measured using a GPC apparatus (GPC "HLC-8020" manufactured by Tosoh Corporation) under conditions of a column temperature of 40°C and a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent, and is expressed in terms of standard polystyrene. Three columns manufactured by Tosoh Corporation under the trade names TSK-GELG5000HHR, G4000HHR, and G3000HHR are used in this example.

[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, there is a tendency that the texture is easily maintained. Furthermore, when the melt viscosity of the acrylic compound is 1000 Pa·s or less, when the acrylic compound is emulsified or dispersed to form a water repellent composition, the acrylic compound can be prevented from precipitating or settling, and therefore the storage stability of the water repellent composition tends to be easily maintained. Note that the melt viscosity at 105°C is more preferably 500 Pa·s or less. In this case, sufficient water repellency is exhibited while the texture is also improved.

[0104] The "melt viscosity at 105°C" is determined by using an elevated flow tester (e.g., Shimadzu CFT-500) to place 1 g of a non-fluorinated polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm), holding the temperature at 105°C for 6 minutes, and measuring the melt viscosity at 100 kgf / cm using a plunger. ２ This refers to the viscosity measured when a load of 1000 kJ / cm is applied.

[0105] (Silicone-based compound) The silicone-based compound is, for example, at least one of a silicone resin and a silicone oil. Among these 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.

[0106] The silicone resin may be an organopolysiloxane containing MQ, MDQ, MT, MTQ, MDT, or MDTQ as a constituent, being solid at 25°C, and having a three-dimensional structure, wherein M, D, T, and Q are each (R''). ３ SiO ０．５ Units, (R'') ２ SiO unit, R″SiO １．５ Units and SiO ２ 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 also have moieties designated as MDQ, MTQ, or MDTQ.

[0108] Silicone resins are also available as solutions in suitable solvents, such as relatively low molecular weight methylpolysiloxanes, 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 (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and decamethylcyclopentasiloxane), KF7312F (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and octamethylcyclotetrasiloxane), KF9021L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), and KF7312L (a 50:50 mixture of trimethylsilyl group-containing polysiloxane and low-viscosity methylpolysiloxane), all of which are commercially available from Shin-Etsu Chemical Co., Ltd.

[0110] Examples of silicone resins that can be used alone include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (trimethylsilyl group-containing polysiloxane, polypropylsilsesquioxane), both of which are commercially available from Dow Corning Toray Co., Ltd. The above commercially available products contain trimethylsilyl group-containing polysiloxanes, and include MQ, MDQ, MT, MTQ, MDT, or MDTQ.

[0111] Silicone oil is linear organopolysiloxane, and can have organic group at least in either the side chain or end of organopolysiloxane.As this silicone oil, the same thing as hydrophobic silicone oil and functionalized silicone oil can be used, for example, can list straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil; modified silicone oil such as amino-modified silicone oil, epoxy-modified silicone oil, carbinol-modified silicone oil, mercapto-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, aralkyl-modified silicone oil, alkylaralkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher aliphatic amide-modified silicone oil.

[0112] The amino-modified silicone oil may be a compound having an organic group containing an amino group and / or an imino group at least on the side chain or terminal of an organopolysiloxane. Such an organic group may be —R—NH ２ an organic group represented by —R—NH—R′—NH ２ Examples of suitable organic groups include organic groups represented by the formula: R and R' include divalent groups such as an ethylene group and a propylene group. Some or all of the amino groups and / or imino groups may be blocked amino groups and / or imino groups. Blocked amino groups and / or imino groups can be obtained, for example, by treating the amino groups and / or imino groups with a blocking agent. Examples of blocking agents include fatty acids having 2 to 22 carbon atoms, acid anhydrides of fatty acids having 2 to 22 carbon atoms, acid halides of fatty acids having 2 to 22 carbon atoms, and aliphatic monoisocyanates having 1 to 22 carbon atoms.

[0113] From the viewpoint of water repellency, the functional group equivalent weight 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 preferably 10 to 100,000 mm ２ / s, and 10 to 30,000 mm ２ / s, and more preferably 10 to 5,000 mm ２ More preferably, the kinematic viscosity at 25°C is 100,000 mm / s. ２ If the kinematic viscosity is greater than 1 / s, the viscosity will be too high and workability will tend to be poor. The kinematic viscosity at 25°C refers to the value measured by the method described in JIS K2283:2000 (Ubbelohde viscometer).

[0115] The amino-modified silicone oil is readily available as a commercially available product. Examples of commercially available products include KF8005, KF-868, KF-864, KF-393, and KF-8021 (all of which are product names of Shin-Etsu Chemical Co., Ltd.), TSF-4709 and XF42-B1989 (product names of Momentive Performance Materials Japan Co., Ltd.), BY16-872, SF-8417, BY16-853U, and BY16-892 (product names of Dow Corning Toray Co., Ltd.), KF-8010 (product name of Shin-Etsu Chemical Co., Ltd.), and WACKER (registered trademark) FINISH WR 301 (product name of Wacker Asahi Kasei Silicones).

[0116] Silicone oils other than amino-modified silicone oils are also readily available as commercially available products. Examples of commercially available products include KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: epoxy-modified silicone oil), X-22-3701E (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: carboxyl-modified silicone oil), SF8428 (manufactured by Dow Corning Toray Co., Ltd., trade name: carbinol-modified silicone oil), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil), and X-22-715 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: methyl hydrogen silicone oil). , higher fatty acid ester-modified silicone oil), KF-96-3000cp (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, dimethyl silicone oil), SF8416 (manufactured by Dow Corning Toray Co., Ltd., trade name, alkyl-modified silicone oil), SH203 (manufactured by Dow Corning Toray Co., Ltd., trade name, alkylaralkyl-modified silicone oil), and SF8410 (manufactured by Dow Corning Toray Co., Ltd., trade 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), the structural units may be arranged in blocks, randomly, or alternately.

[0118] [In formula (1), R ２０ , R ２１ and R ２２ are each independently a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and R ２３ is a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 8 to 40 carbon atoms, and R ３０ , R ３１ , R ３２ , R ３３ , R ３４ and R ３５are each independently a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms; a is an integer of 0 or more; b is an integer of 1 or more; (a+b) is 10 to 200; when a is 2 or more, a plurality of R ２０ and R ２１ may be the same or different, and when b is 2 or more, a plurality of R ２２ and R ２３ may be the same or different.

[0119] In the organo-modified silicone, the alkoxyl group having 1 to 4 carbon atoms may be linear or branched. Examples of the alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. R ２０ , R ２１ and R ２２ are each independently preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0120] Examples of the hydrocarbon group having 8 to 40 carbon atoms and having an aromatic ring include an aralkyl group having 8 to 40 carbon atoms and a group represented by the following general formula (2) or (3).

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

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

[0123] [In formula (3), R ４２ is an alkylene group having 2 to 6 carbon atoms, and R ４３ is a single bond or an alkylene group having 1 to 4 carbon atoms, and d is an integer of 0 to 3. When d is 2 or 3, there are multiple R４３ may be the same or different.]

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

[0125] Examples of the aralkyl group having 8 to 40 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylethyl group, etc. Among these, the phenylethyl group and the phenylpropyl group are preferred in terms of ease of industrial production and availability.

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

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

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

[0129] The 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, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, behenyl, hexacosyl, octacosyl, triacontyl, and dotriacontyl. 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, in terms of improving water repellency. The fewer carbon atoms in the alkyl group, the better the chalk mark resistance. Furthermore, the greater the carbon number in the alkyl group, the better the water repellency. Furthermore, if the carbon number exceeds 40, the stability of the dispersion tends to decrease. Furthermore, if the carbon number is less than 8, the 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 and an aromatic ring, or an alkyl group having 3 to 22 carbon atoms. ３０ , R ３１ , R ３２ , R ３３ , R ３４ and R ３５ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0131] In the organo-modified silicone, a is an integer of equal to or greater than 0. In terms of ease of industrial production, availability, and superior peel strength, a is preferably equal to or less than 40, and more preferably equal to or less than 30.

[0132] In organo-modified silicones, (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the production and handling of the silicone itself tends to be easier.

[0133] Organo-modified silicones can be synthesized by conventionally known methods, for example, by subjecting silicone having SiH groups to a hydrosilylation reaction with an aromatic compound and / or an α-olefin having a vinyl group.

[0134] Examples of the silicone having a SiH group include methylhydrogensilicone and a copolymer of dimethylsiloxane and methylhydrogensiloxane, each having a degree of polymerization of 10 to 200. Among these, methylhydrogensilicone is preferred because it is easy to produce industrially and is readily available.

[0135] The aromatic compound having a vinyl group is represented by R ２３ In the above formula, the aromatic compound is a compound from which a hydrocarbon group having 8 to 40 carbon atoms and an aromatic ring is derived. Examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.

[0136] The above α-olefin is represented by R in the above general formula (1). ２３ In the above formula, the α-olefin is a compound from which an alkyl group having 8 to 40 carbon atoms is derived. Examples of the α-olefin include α-olefins having 8 to 40 carbon atoms such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), and 1-dotriacontene (C32).

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

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

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

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

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

[0142] As the non-fluorine-based water-repellent component, from the viewpoints of water repellency and chalk mark prevention, it is preferable to use the above-mentioned acrylic compound and the above-mentioned silicone compound in combination. The mass ratio of the acrylic compound (α) to the silicone compound (β) is not particularly limited. For example, when the silicone compound (β) is a silicone resin, the silicone compound (β) may account for 1 to 99 parts by mass, assuming the total of the acrylic compound (α) and the silicone compound (β) to be 100 parts by mass. The ratio is preferably 5 to 98 parts by mass, more preferably 10 to 97 parts by mass, and even more preferably 15 to 95 parts by mass. Having the proportion of the silicone compound (β) within this range results in excellent water repellency and Bundesmann water repellency after wear. Alternatively, when the silicone compound (β) is an organo-modified silicone, the silicone compound (β) may account for 10 to 90 parts by mass, assuming the total of the acrylic compound (α) and the silicone compound (β) to be 100 parts by mass. The content is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass. When the proportion of the silicone compound (β) is within this range, excellent water repellency is achieved and chalk marks are less likely to occur.

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

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

[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 viewpoints of water repellency, durable water repellency, and texture, the normal alkanes are preferably triacontane, hentriacontane, and dotriacontane.

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

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

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

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

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

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

[0152] Examples of the aliphatic polyisocyanate constituting the aliphatic polyisocyanate derivative (U1) include aliphatic diisocyanates such as hexamethylene diisocyanate (hexane diisocyanate) (HDI), pentamethylene diisocyanate (pentane diisocyanate) (PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3- or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. In the present application, the term "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 a mixture thereof (H12MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

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

[0156] The aliphatic polyisocyanate derivative is preferably at least one of an isocyanurate derivative, a trimethylolpropane adduct, an allophanate derivative, and a biuret derivative, and more preferably an isocyanurate derivative. When the aliphatic polyisocyanate derivative contains an isocyanurate derivative, the texture becomes good.

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

[0158] The aliphatic polyisocyanate derivatives may be used alone or in combination of two or more. Preferred examples include the use of an isocyanurate derivative of hexamethylene diisocyanate alone, or the use of an isocyanurate derivative of hexamethylene diisocyanate in combination with at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. In this case, the blending ratio of the isocyanurate derivative of hexamethylene diisocyanate is, for example, 60 parts by mass or more relative to 100 parts by mass of the total amount of the isocyanurate derivative of hexamethylene diisocyanate and at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate. The blending ratio of at least one selected from the group consisting of an isocyanurate derivative of bis(isocyanatomethyl)cyclohexane, a trimethylolpropane adduct of hexamethylene diisocyanate, an allophanate derivative of hexamethylene diisocyanate, and a biuret derivative of hexamethylene diisocyanate is, for example, 15 parts by mass or more and, for example, 40 parts by mass or less, preferably 30 parts by mass or less.

[0159] The aliphatic polyisocyanate derivative can be produced by a known method.

[0160] The average number of isocyanate groups in the 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 equal to or greater than the lower limit, water repellency can be further improved. The average number of isocyanate groups is calculated by the following formula (1) from the isocyanate group concentration A of the aliphatic polyisocyanate derivative, the solid content concentration B, and the number average molecular weight C measured by gel permeation chromatography using the following equipment and conditions. When two or more types of aliphatic polyisocyanate derivatives are used in combination, the average number of isocyanate groups is calculated from the weight ratio of the aliphatic polyisocyanate derivatives and the average number of isocyanate functional groups thereof.

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

[0162] (Conditions for measuring number average molecular weight) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: TSKgel G1000HXL, TSKgel G2000HXL, and TSKgel G3000HXL (manufactured by Tosoh Corporation) connected in series Detector: differential refractometer Injection volume: 100 μL Eluent: tetrahydrofuran Flow rate: 0.8 mL / min Temperature: 40° C. Calibration curve: standard polyethylene oxide in the range of 106 to 22450 (manufactured by Tosoh Corporation, trade name: TSK standard polyethylene oxide)

[0163] The long-chain active hydrogen compound has both a hydrocarbon group having 12 to 30 carbon atoms and an active hydrogen group that reacts with an aliphatic polyisocyanate derivative.

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

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

[0168] The branched-chain saturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain saturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include branched-chain saturated hydrocarbon group-containing alcohols such as isomyristyl alcohol, isocetyl alcohol, isostearyl alcohol, and isoicosyl alcohol.

[0169] The linear unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a linear unsaturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include linear unsaturated hydrocarbon group-containing alcohols such as tetradecenyl alcohol, hexadecenyl alcohol, oleyl alcohol, icosenyl alcohol, docosenyl alcohol, tetracosenyl alcohol, hexacosenyl alcohol, and octacosenyl alcohol.

[0170] The branched-chain unsaturated hydrocarbon group-containing active hydrogen compound is an active hydrogen compound containing a branched-chain unsaturated hydrocarbon group having from 12 to 30 carbon atoms, and examples thereof include 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 compounds can be used alone or in combination of two or more.

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

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

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

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

[0176] The cationic active hydrogen compound has both an active hydrogen group and a cationic group. The cationic active hydrogen compound can be used alone or in combination of two or more kinds.

[0177] As described above, the active hydrogen group is an active hydrogen group that reacts with an aliphatic polyisocyanate derivative, and examples thereof include hydroxyl groups. The cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule. Furthermore, examples of the cationic group include tertiary amino groups. That is, the cationic active hydrogen compound preferably has two or more hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. More preferably, the cationic active hydrogen compound has two hydroxyl groups per molecule as the active hydrogen group and a tertiary amino group as the cationic group. Such a cationic active hydrogen compound can impart good dispersibility in water and can also introduce cationic groups that have affinity for fibers, thereby improving washing durability.

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

[0179] The acid compound is a compound that forms a salt with a cationic group. Examples of the acid compound include one or both of an organic acid and an inorganic acid. Examples of the organic acid include acetic acid, lactic acid, tartaric acid, and malic acid, and preferably acetic acid or lactic acid, and more preferably acetic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and preferably hydrochloric acid. The acid compound is preferably an organic acid. When the acid compound contains an organic acid, the acid volatilizes by heat treatment, thereby reducing ionicity and improving water resistance, thereby improving water repellency. Furthermore, the acid volatilizes by heat treatment, making it easier for the cationic group to adsorb to the fiber, and thereby improving washing durability. The acid compounds can be used alone or in combination of two or more types.

[0180] A urethane-based compound is obtained as a reaction product by reacting the aliphatic polyisocyanate derivative with a long-chain active hydrogen compound, a cationic active hydrogen compound, and an acid compound. To react the aliphatic polyisocyanate derivative with the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound, the long-chain active hydrogen compound is first blended with the aliphatic polyisocyanate derivative, and the aliphatic polyisocyanate derivative is then reacted with the long-chain active hydrogen compound. In this case, for example, when the isocyanurate derivative of the aliphatic polyisocyanate has an average number of isocyanate groups of 3, the long-chain active hydrogen compound is preferably blended so that two isocyanate groups in the isocyanurate derivative of the aliphatic polyisocyanate are modified by the long-chain active hydrogen compound to hydrocarbon groups having 12 to 30 carbon atoms, leaving one isocyanate group in the isocyanurate derivative of the aliphatic polyisocyanate and no unreacted isocyanurate derivative of the aliphatic polyisocyanate. Specifically, the long-chain active hydrogen compound is blended with the aliphatic polyisocyanate derivative so that the equivalent ratio of isocyanate groups to active hydrogen groups (isocyanate groups / active hydrogen groups) is, for example, 1.2 or more, preferably 1.5 or more, and, for example, 2.0 or less. As a result, the molecular terminals of the reaction product of the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound (hereinafter referred to as the first intermediate reaction product) are hydrocarbon groups and isocyanate groups having from 12 to 30 carbon atoms.

[0181] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions include a reaction temperature of, for example, 70°C or higher and 120°C or lower, and a reaction time of 1 hour or higher and 6 hours or lower. 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] In the above reaction, a known solvent such as methyl ethyl ketone can also be added in an appropriate ratio.

[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 so that the equivalent ratio of isocyanate groups to active hydrogen groups in the cationic active hydrogen compound (isocyanate groups / active hydrogen groups) is, for example, 0.95 or more and, for example, 1.05 or less.

[0184] The above reaction is carried out under a nitrogen atmosphere. The reaction conditions include a reaction temperature of, for example, 70°C to 120°C and a reaction time of 0.5 to 4 hours. The above reaction is carried out until the reaction between the first intermediate reaction product and the cationic active hydrogen compound is complete. A known solvent, such as methyl ethyl ketone, can also be added to the above reaction in an appropriate ratio. This results in a reaction product (hereinafter referred to as the second intermediate reaction product) between the first intermediate reaction product and the cationic active hydrogen compound. The second intermediate reaction product has a hydrocarbon group having from 12 to 30 carbon atoms and a cationic group.

[0185] Next, an acid compound is blended with the second intermediate reaction product. The blending ratio of the acid compound is, for example, 0.5 mol or more, preferably 3 mol or more, and for example, 10 mol or less, preferably 4 mol or less, per mol of cationic group of the cationic active hydrogen compound. This causes the acid compound to form a salt with the cationic group of the second intermediate reaction product, resulting in a reaction liquid containing a reaction product (i.e., a urethane-based compound) of the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound. The reaction product has a hydrocarbon group having from 12 to 30 carbon atoms and a cationic group. Furthermore, because the reaction product has a hydrocarbon group having from 12 to 30 carbon atoms, it can self-disperse (self-emulsify) in water without the need for a dispersant (emulsifier). In other words, the reaction product can be internally emulsified.

[0186] Next, while maintaining the temperature of the reaction liquid at, for example, 50°C or higher and 100°C or lower, water is added to the reaction liquid to emulsify it. Thereafter, the solvent is removed from the reaction liquid. This results in an aqueous dispersion containing the reaction product (i.e., the urethane compound). The solids concentration of the aqueous dispersion is, for example, 10% by mass or higher and, for example, 30% by mass or lower.

[0187] Such urethane compounds are reaction products obtained using long-chain active hydrogen compounds, and therefore have excellent water repellency, oil repellency, oil resistance, and stain resistance. Furthermore, such urethane compounds are reaction products obtained using cationic active hydrogen compounds, and therefore have improved affinity with fibers, resulting in excellent washing durability for fibers.

[0188] In such a urethane-based compound, the concentration of the hydrocarbon group is 30% or more and 85% or less, preferably 50%. If the concentration of the hydrocarbon group is equal to or more than the above-mentioned lower limit, the water repellency can be improved. If the concentration of the hydrocarbon group is equal to or less than the above-mentioned upper limit, the stability of the urethane-based compound can be improved. The concentration of the hydrocarbon group can be calculated from the amount of each component charged.

[0189] In the above description, the aliphatic polyisocyanate derivative and the long-chain active hydrogen compound are first reacted to obtain a reaction liquid containing a first intermediate reaction product, the first intermediate reaction product is then reacted with a cationic active hydrogen compound to obtain a reaction liquid containing a second intermediate reaction product, and the second intermediate reaction product is then reacted with an acid compound. However, the order of the reactions is not particularly limited. For example, the aliphatic polyisocyanate derivative and the cationic active hydrogen compound may be reacted first, and then the long-chain active hydrogen compound and the acid compound may be reacted. Alternatively, the aliphatic polyisocyanate derivative, the long-chain active hydrogen compound, the cationic active hydrogen compound, and the acid compound may be mixed together and reacted.

[0190] (Dendrimer Compound) The dendrimer compound may be, for example, a dendritic polymer compound having a structure that is radially branched regularly from the center. In order to obtain water repellency, the dendritic polymer compound may have a linear or branched hydrocarbon group having one or more carbon atoms at the end of the branch.

[0191] The dendritic polymer compound may be, for example, a "polymer extender" disclosed in International Publication No. 2014 / 160906. For example, a compound obtained by reacting at least one isocyanate group-containing compound selected from isocyanate, diisocyanate, polyisocyanate, or a mixture thereof with at least one isocyanate-reactive compound selected from the group consisting of formulas (Ia), (Ib), and (Ic):

[0192]

[0193] In the above formula, R ５０ are each independently -H, R ５１ , -C(O)R ５１ , -(CH ２ CH ２ O) ｎ (CH (CH ３ ) CH ２ O) ｍ R ５２ , or -(CH ２ CH ２ O) ｎ (CH (CH ３ ) CH ２ O) ｍ C(O)R ５１ where n is independently 0 to 20, m is independently 0 to 20, and m+n is greater than 0. ５１ are each independently a linear or branched alkyl group having 5 to 29 carbon atoms, which may contain one or more unsaturated bonds; R ５２ are each independently —H or a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds.

[0194] In addition, in formula (Ia), R ５０ or R５２ At least one of the groups is —H.

[0195] In the above formula, R ５３ are each independently -H, -R ５１ , -C(O)R ５１ , -(CH ２ CH ２ O(CH(CH ３ ) CH ２ O) ｍ R ５２ , or -(CH ２ CH ２ O(CH(CH ３ ) CH ２ O.C.(O.)R. ５１ and R ５４ are each independently —H, a linear or branched alkyl group having 6 to 30 carbon atoms which may contain one or more unsaturated bonds, —(CH ２ CH ２ O) ｎ’ (CH (CH ３ ) CH ２ O) ｍ’ R ５２ , or -(CH ２ CH ２ O(CH(CH ３ ) CH ２ O.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.

[0196] In addition, in formula (Ib), R ５２ , R ５３ or R ５４ At least one of the groups is —H.

[0197] In the above formula, R ５５ is -H, -C(O)R ５１ , or -CH ２ C[CH ２ OR ５０ ] ３ is.

[0198] In addition, in formula (Ic), R ５５ or R ５０ At least one of the groups 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" (manufactured by Bayer, trade name), "Duranate THA-100" (manufactured by Asahi Kasei Corporation, trade name), and "Duranate 24A-100" (manufactured by Asahi Kasei Corporation, trade name) can be used. The reaction can be carried out, for example, at 80°C for 1 hour or more.

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

[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 of water only. The amount of the aqueous medium may be 30 to 99% by mass or 50 to 90% by mass, with the entire water repellent treatment agent being 100% by mass.

[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 a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. 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.

[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, alkylalkanolamides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, etc. Examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylate salts, alkylbenzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylphenyl ether sulfate salts, vinyl sulfosuccinate, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ether phosphates, etc. Examples of cationic surfactants include amine salts, amidoamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples include, but are not limited to, amine salt surfactants such as alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and quaternary ammonium salt surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Examples of amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amidobetaines, and acetic acid betaine, and specific examples include long-chain amine oxides, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyl dimethylaminoacetic acid betaine.The amount of these surfactants used is not particularly limited, but is preferably 1 to 20% by mass, more preferably 1.5 to 10% by mass, of the solid content of the emulsion.

[0204] The hydrophilic-lipophilic balance (HLB) of the emulsifier is not particularly limited. The average HLB of the nonionic emulsifier in the non-fluorinated water repellent 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 the emulsifier is a value calculated by the Griffin method, assuming that the ethyleneoxy group in the emulsifier is the hydrophilic group.

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

[0206] 2.1.3 Content of non-fluorine-based water-repellent component The content of the non-fluorine-based water-repellent component in the water-repellent treatment agent is not particularly limited. For example, the ratio (mass proportion) of the non-fluorine-based water-repellent component to the entire water-repellent treatment agent may be 0.1 to 70 mass %, or 0.5 to 50 mass %.

[0207] 2.2 Contact Method In one embodiment of the method for producing a textile product, the non-fluorine-based water-repellent component (water-repellent treatment agent containing a non-fluorine-based water-repellent component) is brought into contact with the pretreated textile material, thereby adhering the non-fluorine-based water-repellent component to the textile material. The method for bringing the non-fluorine-based water-repellent component (water-repellent treatment agent containing a non-fluorine-based water-repellent component) into contact with the textile material is not particularly limited. Examples include processing methods such as immersion, spraying, and coating. The immersion method may be a continuous method or a batch method. In the continuous method, first, the non-fluorine-based water-repellent component is diluted in an aqueous solvent to prepare a water-repellent treatment agent (treatment liquid). Next, the object to be treated (textile material) is continuously fed into an impregnation device filled with the treatment liquid, and the object to be treated is impregnated with the treatment liquid, after which unnecessary treatment liquid is removed. The impregnation device is not particularly limited, and a padder, kiss-roll type applicator, gravure coater type applicator, spray type applicator, foam type applicator, coating type applicator, etc. are preferably used, with a padder type being particularly preferred. Subsequently, the solvent remaining on the treated material is removed using a dryer. The dryer is not particularly limited, and a spread-cloth dryer such as a hot flue or tenter is preferred. The continuous method is preferably used when the treated material is in the form of a fabric, such as a woven fabric. On the other hand, the batch method comprises, for example, a step of immersing the treated material in a treatment solution and a step of removing the solvent remaining on the treated material. The batch method is preferably used when the treated material is not in the form of a fabric, such as loose fibers, tops, slivers, hanks, tows, yarns, etc., or when the continuous method is not suitable, such as knitted fabrics. For the immersion step, for example, a cotton dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, etc. can be used. In the operation for removing the solvent, a cheese dryer, a beam dryer, a hot air dryer such as a tumble dryer, a high frequency dryer, or the like can be used.

[0208] 2.3 Heat Treatment After the water-repellent component is applied to the textile material, it is preferable to heat treat it as appropriate. There are no particular restrictions on the temperature conditions, but mild conditions of 100 to 130°C can be used to impart sufficiently good water repellency to the textile product. The temperature conditions may be high-temperature treatment at 130°C or higher (preferably up to 200°C), and in such cases, it is possible to shorten the treatment time compared to when a fluorine-based water repellent agent is used. Therefore, according to the textile product manufacturing method disclosed herein, deterioration of the textile product due to heat is suppressed, the texture of the textile product becomes soft during the water-repellent treatment, and sufficient water repellency can be imparted to the textile product under mild heat treatment conditions, i.e., low-temperature curing conditions.

[0209] 2.4 Amount of Deposit A ​​non-fluorinated water-repellent component is deposited on the textile material after the water-repellent treatment. The treatment with the water-repellent treatment agent is preferably carried out in an amount such that the amount of the non-fluorinated water-repellent component deposited is 0.1 to 10 parts by mass, or 0.5 to 5 parts by mass, per 100 parts by mass of the textile material. Within this range, durable water repellency and texture can both be achieved at high levels.

[0210] 3. Use of a Crosslinking Agent in Combination In one embodiment, when improving durable water repellency is particularly desired, the method for producing a textile product preferably includes, in addition to performing the pretreatment and water repellency treatment on the above-described textile material, attaching a crosslinking agent containing methylol melamine or a compound having two or more isocyanate groups or blocked isocyanate groups to the textile material and heating it. Furthermore, when further improving durable water repellency, it is preferable that the pretreatment agent or water repellency treatment agent contains a non-fluorine-based polymer copolymerized with a monomer having a functional group reactive with the above-described crosslinking agent. Examples of compounds having two or more isocyanate groups are as described above. The crosslinking agent may be used alone or in combination.

[0211] The crosslinking agent can be attached to the object to be treated (textile product) by, for example, immersing the object to be treated in a treatment liquid in which the crosslinking agent is dissolved in an organic solvent or emulsified and dispersed in water, and then drying the treatment liquid attached to the object to be treated. The crosslinking agent attached to the object to be treated can then be heated to promote a reaction between the crosslinking agent and the object to be treated and the non-fluorine-based water-repellent component. To promote the crosslinking agent reaction sufficiently and more effectively improve durable water repellency, the heating is preferably performed at 110 to 180°C for 1 to 5 minutes. The process of attaching the crosslinking agent and heating may be performed simultaneously with the process of treating with the water-repellent treatment agent described above. When performed simultaneously, for example, a second treatment liquid containing a non-fluorine-based water-repellent component and a crosslinking agent is attached to the object to be treated, the water is removed, and then the crosslinking agent attached to the object to be treated is heated. Considering simplification of the water-repellent treatment process, reduction of heat consumption, and economic efficiency, it is preferable to perform the process simultaneously with the treatment process using the second treatment liquid.

[0212] However, excessive use of the crosslinking agent may impair the feel, and the crosslinking agent is preferably used in an amount of 0.01 to 50 parts by mass, or 0.1 to 10 parts by mass, per 100 parts by mass of the material to be treated (textile product).

[0213] 4. Applications The textile products manufactured through the above pretreatment and water-repellent treatment have excellent water repellency (initial water repellency, durable water repellency, Bundesmann water repellency, and water repellency of natural fibers). Furthermore, since these textile products do not use fluorine-based compounds, they can be considered environmentally friendly. Because of their excellent water repellency, these textile products are suitable for a variety of applications, including clothing and non-clothing items, such as down jacket coverings, coats, blousons, windbreakers, blouses, dress shirts, skirts, slacks, gloves, hats, futon coverings, futon drying rack covers, curtains, and tents.

[0214] As described above, one embodiment of the technology of the present disclosure has been described, but the technology of the present disclosure can be modified in various ways other than the above embodiment without departing from the gist thereof. Below, the technology of the present disclosure will be described in more detail while showing examples, but the technology of the present disclosure is not limited to the following examples.

[0215] 1. Preparation of Pretreatment Agent A treatment liquid containing the following isocyanate compound was prepared as a pretreatment agent.

[0216] (Preparation Example A-1: ​​HDI trimer) Duranate TPA-100 (an isocyanurate type of hexamethylene diisocyanate, Asahi Kasei, NCO group content: 23.1%, NV: 100%) was prepared as a polyisocyanate.

[0217] (Preparation Example A-2: IPDI trimer) In a reactor equipped with a stirrer, thermometer, cooler, 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 and propylene glycol diacetate (Dowanol (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed at room temperature to completely dissolve the polyisocyanate, thereby obtaining a PGDA solution of IPDI trimer. Next, 4.3 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) was mixed with the PGDA solution. To this was added 12.8 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 7 mol) as an emulsifier, and the mixture was mixed while being appropriately cooled so that the temperature of the mixture became 50°C or less, thereby obtaining a solution containing 40% by mass of IPDI trimer.

[0218] (Preparation Example A-3: IPDI trimer / HDI trimer nurate) In a reactor similar to that used in Preparation Example A-2, 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%) as a polyisocyanate and 10 parts by mass (NCO equivalent: 0.62 mol) of an isocyanurate of hexamethylene diisocyanate (HDI) (Duranate TPA-100, manufactured by Asahi Kasei Corporation, NCO group content: 23.1%, NV: 100%) 98 parts by mass (NCO equivalent: 0.825 mol) and propylene glycol diacetate (Dowanol (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed to completely dissolve the polyisocyanate, and a PGDA solution of IPDI trimer / HDI trimer was obtained. Next, 4.0 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) was mixed with the solution. Next, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 10 mol) as an emulsifier was added, and the mixture was mixed while appropriately cooling so that the temperature of the mixture was 50 ° C. or less, 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 a reactor similar to that used in Preparation Example A-2, 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%) as a polyisocyanate and 10 parts by mass (NCO equivalent: 0.62 mol) of a biuret type (Duranate) of hexamethylene diisocyanate (HDI) were mixed at room temperature. 24A-100, manufactured by Asahi Kasei Corporation, NCO group content: 23.5%, NV: 100%), 98 parts by mass (NCO equivalent: 0.839 mol), and propylene glycol diacetate (Dowanol (registered trademark) PGDA, Ando Parachemie Co., Ltd.) as a solvent were mixed to completely dissolve the polyisocyanate, and a PGDA solution of IPDI trimer / HDI trimer was obtained. Next, 4.0 parts by mass of N,N-dimethylcyclohexylamine (Kanto Chemical Co., Ltd.) was mixed with the solution. Next, 11.9 parts by mass of polyoxyethylene tridecyl ether phosphate (Rhodafac (registered trademark) range, manufactured by Rhodia, EO: 10 mol) as an emulsifier was added, and the mixture was mixed while appropriately cooling so that the temperature of the mixture was 50 ° C. or less, to obtain a solution containing 70% by mass of IPDI trimer / HDI trimer biuret.

[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 product of 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 Vestanat 1890 / 100 (isophorone diisocyanate trimer, manufactured by Evonik, NCO group content: 17.3%, NV: 100%) as a polyisocyanate and 150 parts by mass of diethylene glycol ethyl methyl ether (hereinafter sometimes abbreviated as MEDG) as a solvent were mixed at room temperature, and 59.6 parts by mass (0.62 mol) of dimethylpyrazole (DMP) as a blocking agent was added in several portions so that the temperature of the reaction solution did not exceed 50°C, and the mixture was stirred for 1 hour. Thereafter, by measuring the Fourier transform infrared (FT-IR) spectrum, it was confirmed that the peak derived from the NCO group (near 2260 cm-1) had disappeared, confirming that the product had been blocked. Next, 21 parts by mass of NIKKOL BC-25 (HLB=18.5, manufactured by Nikko Chemicals Co., Ltd.) and pure water were added little by little while mixing to obtain a dispersion containing 20% ​​by mass of DMP-blocked IPDI trimer.

[0222] Comparative Preparation Example: Anionic Compound A resin dispersion containing an anionic compound (dihydroxydiphenyl sulfone / formaldehyde condensate, weight average molecular weight 40,000, manufactured by OG-G Nagase Color Chemicals Co., Ltd., SZ9904, solid content 33%) and 0.5 mL / L of acetic acid (80% by mass aqueous solution) was prepared.

[0223] 2. Preparation of Water-Repellent Treatment Agent A treatment liquid containing the following non-fluorine-based water-repellent component was prepared as a water-repellent treatment agent.

[0224] 2.1 Preparation of Dispersion of Acrylic Compound (Preparation Example B-1) 15.6 parts by mass of stearyl acrylate, 0.4 parts by mass of diacetone acrylamide, 0.8 parts by mass of Noigen XL-100 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 14.7), 0.2 parts by mass of stearyl trimethylammonium sulfate, 10 parts by mass of tripropylene glycol, and 68.8 parts by mass of water were placed in an autoclave and mixed and stirred at 45 ° C. to obtain a mixed solution. Ultrasonic waves were irradiated to this mixed solution to emulsify and disperse all the 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 into the autoclave to maintain the internal pressure of the autoclave at 0.3 MPa, and 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 According to the amounts of ingredients shown in Table 1 below, dispersions containing 20% ​​by mass of acrylic resin were obtained in the same manner as in Preparation Example B-1.

[0226]

[0227] 2.2 Preparation of silicone compound dispersion 2.2.1 Alkyl-modified silicone dispersion (Preparation Example B-4: Octadecyl dimethicone dispersion) SiH:SiCH ３ Methyl hydrogen silicone with a molar ratio of 5:5 (measured by 1H NMR (nuclear magnetic resonance)) and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were charged into a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-octadecene was added dropwise to the mixture in the flask relative to 1 molar equivalent of the reactive group (Si—H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain the compound represented by the formula (1) below, R ２０ , R ２１ and R ２２ is CH ３ and R ２３ is C １８ H ３７a is 40, b is 40, a:b is 1:1, and R ３０ ~R ３５ is CH ３ Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to Fourier transform infrared (FT-IR) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

[0228]

[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 Noigen XL-40 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 10.5), 0.5 parts by mass of Noigen XL-60 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene branched decyl ether, HLB = 12.5), 0.5 parts by mass of stearyl trimethylammonium sulfate, and 10 parts by mass of dipropylene glycol were mixed with heating. Next, 66.0 parts by mass of water was added little by little to the obtained mixture while mixing, to obtain a dispersion containing 20% ​​by mass of octadecyl dimethicone (average HLB of nonionic surfactants = 11.4).

[0230] (Preparation Example B-5: Hexacosyl Dimethicone Dispersion) SiH:SiCH ３ Methyl hydrogen silicone with a molar ratio of 4:6 (measured by 1H NMR (nuclear magnetic resonance)) and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were charged into a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-hexacosene was added dropwise to the mixture in the flask relative to 1 molar equivalent of the reactive group (Si—H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain the compound represented by the formula (1) above, R ２０ , R ２１ and R ２２ is CH３ and R ２３ is C ２６ H ５３ a is 60, b is 90, a:b is 2:3, and R ３０ ~R ３５ is CH ３ Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to Fourier transform infrared (FT-IR) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen silicone had disappeared.

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

[0232] (Preparation Example B-6: Dotriacontyl Dimethicone Dispersion) SiH:SiCH ３ Methyl hydrogen silicone with a molar ratio of 3:7 (measured by 1H NMR (nuclear magnetic resonance)) and a mixed solution of platinum (IV) chloride in ethylene glycol monobutyl ether and toluene as a hydrosilylation catalyst were charged into a flask so that the platinum concentration relative to the reactants in the system was 5 ppm. The atmosphere in the flask was replaced with nitrogen, and 1 molar equivalent of 1-dotriacontene was added dropwise to the mixture in the flask relative to 1 molar equivalent of the reactive group (Si—H) of the methyl hydrogen silicone. The inside of the vessel was heated to 120°C, and an addition reaction was carried out for 6 hours to obtain the compound represented by the formula (1) above, R ２０ , R ２１ , R ２２ is CH ３ and R ２３ is C ３２ H ６５ a is 140, b is 60, a:b is 7.3, and R ３０ ~R ３５ is CH ３ Completion of the addition reaction was confirmed by subjecting the resulting alkyl-modified silicone to Fourier transform infrared (FT-IR) spectroscopic analysis and confirming that the absorption spectrum derived from the SiH group of the methyl hydrogen 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 the nonionic surfactants = 8.1).

[0234] Table 2 below shows the compositions of Preparation Examples B-4 to B-6 and the average HLB of the nonionic surfactants.

[0235]

[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 Dow Corning Toray Co., Ltd., trade name) as the silicone resin and 13.4 parts by mass of KF-96A-100cs (manufactured by Shin-Etsu Silicones Co., Ltd.) as the 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 uniform solution, 0.8 parts by mass of KF-8012 (manufactured by Shin-Etsu Chemical Co., Ltd., both terminal amino-modified silicone, functional group equivalent 2200) as the amino-modified silicone was added to obtain a mixture. Next, 1.6 parts by mass of Noigen XL-40 was added, and 78.4 parts by mass of water was added little by little while mixing. The mixture was subjected to ultrasonic treatment at 60 to 70°C for 10 minutes using an ultrasonic emulsifier, and then cooled to room temperature to obtain a dispersion containing 20% ​​by mass of a silicone-based compound (average HLB of the nonionic surfactants = 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 blending ratios shown in Table 3 below were used (average HLB of the nonionic surfactants = 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 blending ratios shown in Table 3 below were used (average HLB of the nonionic surfactants = 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 blending ratios shown in Table 3 below were used (average HLB of the nonionic surfactants = 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 Wacker Asahi Kasei Silicones, amine equivalent 3700, solids content 100%) was used as the amino-modified silicone and the blending ratio shown in Table 3 below was used (average HLB of the nonionic surfactants = 12.0).

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

[0242] The nonionic surfactants are SPAN65 (HLB 2.1, manufactured by Croda), Noigen XL-160 (HLB 16.3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and NIKKOL BC-30 (HLB 19.5, manufactured by Nikko Chemicals Co., Ltd.). Noigen XL-40 is as described above.

[0243] 2.3 Preparation of Wax Compound Dispersion (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. Next, the temperature inside the vessel was raised to 110-120°C with stirring. Thereafter, high-pressure emulsification was performed for 30 minutes while maintaining high pressure inside the vessel, and an emulsion containing 20% ​​by mass of paraffin wax was obtained (average HLB of nonionic surfactants = 9.7).

[0244] 2.4 Preparation of Urethane Compound Dispersion 2.4.1 Synthesis of Polyurethane Resin (Synthesis Example U-1) In a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube, 500 parts by mass of 1,6-hexamethylene diisocyanate (HDI, manufactured by Mitsui Chemicals, Inc., product name: Takenate 700), 0.25 parts by mass of 2,6-di(tert-butyl)-4-methylphenol (also known as dibutylhydroxytoluene, BHT, hindered phenol-based antioxidant), and 0.25 parts by mass of tetraphenyl dipropylene glycol diphosphite (organic phosphite ester, cocatalyst) were mixed under a nitrogen atmosphere. 10.7 parts by mass of 1,3-butanediol was then added to the mixture, and nitrogen was introduced into the liquid phase for 1 hour. The mixture was then heated to 80°C and reacted for 3 hours, after which the temperature was lowered to 60°C. Thereafter, 0.2 parts by mass of trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate was added as an isocyanuration catalyst, and the mixture was allowed to react for 1.5 hours. Subsequently, 0.04 parts by mass of o-toluenesulfonamide was added per 100 parts by mass of HDI. The reaction mixture was then passed through a thin-film distillation apparatus (temperature 150°C, vacuum degree 93.3 Pa) and distilled until the amount of residual HDI monomer was 0.5% or less, yielding an aliphatic polyisocyanate derivative (isocyanurate derivative of hexamethylene diisocyanate). The resulting aliphatic polyisocyanate derivative had an isocyanate group content of 20.9% and an average isocyanate functionality of 3.0.

[0245] 2.4.2 Preparation of Polyurethane Resin Dispersion (Preparation Example B-14) In a reactor equipped with a stirrer, thermometer, cooler, and nitrogen gas inlet tube, 100.08 parts by mass of the aliphatic polyisocyanate derivative of Synthesis Example U-1 as an aliphatic polyisocyanate derivative and 90.03 parts by mass of Kalcol 8098 (stearyl alcohol, manufactured by Kao Corporation) as a long-chain active hydrogen compound were mixed and reacted in a nitrogen atmosphere at 110°C for 4 hours until the isocyanate group concentration reached 3.67%. Next, the reaction solution was cooled to 80°C, and 9.89 parts by mass of N-methyldiethanolamine as a cationic active hydrogen compound was added, followed by a reaction at 80°C for 1 hour. 50 parts by mass of methyl ethyl ketone was added as a solvent, and the reaction was continued at 80°C until disappearance of the 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 solution, and the temperature was raised to 80°C. The reaction solution was mixed until completely dissolved, and then cooled to 75°C. Thereafter, 18.93 parts by mass of acetic acid was added as an acid compound to neutralize. 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. Next, MEK was distilled off using an evaporator at a water bath temperature of 60°C under reduced pressure. Next, the solids concentration was adjusted to 20% by mass with ion-exchanged water, thereby obtaining a dispersion containing a polyurethane resin (average HLB of nonionic surfactants = 9.0, solids content 20% by mass).

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

[0247] 52.7 parts by weight of water, 0.7 parts by weight of ARMEEN DM-18D, 2.0 parts by weight of TERGITOL TMN-10, and 0.6 parts by weight of acetic acid were added to a beaker and stirred to prepare a surfactant solution, which was then heated to 60°C. The dendrimer solution prepared above was cooled to 60°C, and the heated surfactant solution was slowly added to prepare a cloudy emulsion. After homogenization at 41.37 MPa (6000 psi), the solvent was removed by distillation under reduced pressure, yielding a dispersion containing 20% ​​dendrimer-based compound (average HLB of nonionic surfactants = 14.4, solids content 20% by weight).

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

[0249] 3.1 Separate-bath treatment (Examples 1 to 22, Comparative Example 1) A first treatment liquid was prepared by diluting an isocyanate compound dispersion with water to obtain the composition (mass %) shown in Table 4 or 5 below, and a treated cloth was then immersed in the first treatment liquid to perform pretreatment. After the pretreatment, the cloth was dried at 130°C for 1 minute to obtain a treated cloth (first treated cloth) treated with the first treatment liquid. Thereafter, a second treatment liquid was prepared by diluting a water-repellent component dispersion with water to obtain the composition shown in Table 4 or 5, and a water-repellent treatment was performed by immersing the first treated cloth in the second treatment liquid. 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.

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

[0252] 4. Evaluation method 4.1 Evaluation of initial water repellency of textile products Tests were conducted in accordance with the spray method of JIS L1092 (2009) with shower water at a temperature of 20°C to evaluate the water repellency of the above textile products. The results were visually evaluated using the following grades. If the characteristics were slightly good, a "+" was given to the grade, and if the characteristics were slightly poor, a "-" was given to the grade. Water repellency: Condition 5: No adhesion or wetting of the surface 4: Slight adhesion or wetting of the surface 3: Partial wetting of the surface 2: Wetting of the surface 1: Wetting of the entire surface 0: Complete wetting of both the front and back surfaces

[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 rating as above.

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

[0255] 4.3.2 Evaluation of Initial and Durable Water Repellency of Abraded Fabrics The water repellency of the above abraded fabrics was evaluated using the same procedure and rating as above.

[0256] 4.4 Bundesmann Rain Test The water repellency, water absorption, and water absorption rate were evaluated for each of the textile products before abrasion (before washing), after washing, and after abrasion, after a rain test according to the method described in JIS L1092:2009 7.3 Rain Test (Shower Test) Method A. The rainfall time was 10 minutes. The water repellency was graded from 1 to 5 according to the wet conditions shown in Figure 1. The higher the score, the better the result. A + (-) next to the grade indicates that the respective property was slightly better (worse).

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

[0258]

[0259]

[0260] The results shown in Tables 4 and 5 reveal the following: (1) When a textile material is pretreated with an isocyanate compound and then subjected to a water-repellent treatment using a non-fluorinated water-repellent component in a separate bath (Examples 1 to 21), the textile product's washing-durable water repellency, the Bundesmann rainfall test, and the water repellency of natural fibers are improved compared to when the water-repellent treatment is performed in a single bath (Comparative Examples 2 and 3). (2) The effect of the separate bath treatment is superior when an unblocked isocyanate is used as the isocyanate compound in the pretreatment (Example 2) compared to when a blocked isocyanate is used (Example 6). (3) When low-temperature drying is performed after the water-repellent treatment, a comparison between separate bath treatment (Example 22) and same bath treatment (Comparative Example 5) shows that separate bath treatment ensures sufficient washing-durable water-repellent performance.

[0261] From the above results, it can be said that a textile product having excellent water repellency can be produced by a method for producing a textile product which includes contacting a textile material with an isocyanate compound and contacting the textile material after contacting with the isocyanate compound with a non-fluorinated water-repellent component.

[0262] In the above examples, an embodiment in which water repellency is imparted to a textile product using an isocyanate group-containing compound and a non-fluorinated water repellent composition is illustrated, but the technology of the present disclosure is not limited to this embodiment. The treatment method of the present disclosure is believed to be capable of imparting excellent initial water repellency and durable water repellency to various articles other than textile products. In particular, as shown in the above examples, the method is suitable for imparting durable water repellency, Bundesmann water repellency, and water repellency to natural fibers to textile products.

Claims

1. A method for producing a textile product, comprising: bringing a textile material into contact with an isocyanate compound; and bringing the textile material, after contact with the isocyanate compound, into contact with a non-fluorinated water-repellent component.

2. The method for producing a textile product according to claim 1, wherein the isocyanate compound is a polyisocyanate.

3. The method for producing a textile product according to claim 1 or 2, wherein the isocyanate compound is at least one of an aliphatic isocyanate, an aromatic isocyanate, an aromatic aliphatic isocyanate, and an alicyclic isocyanate.

4. The method for producing a textile product according to any one of claims 1 to 3, wherein the isocyanate compound is a non-blocked isocyanate.

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

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