TW202001035A - Water repellent agent, water repellent fiber product, and method for manufacturing same - Google Patents

Abstract

Provided is a water repellent agent which imparts excellent water repellency to fibers without significantly reducing the flame retardancy thereof. The water repellent agent is an aqueous dispersion containing at least: a hydrocarbon compound having a functional group capable of reacting with an isocyanate group; and an isocyanate compound dispersed in water, wherein the molar ratio of a crosslinkable functional group in the isocyanate compound to the functional group in the hydrocarbon compound is at least 0.3.

Description

Water-repellent agent, water-repellent fiber product and manufacturing method thereof

Field of invention The invention relates to a water-repellent agent, a water-repellent fiber product and a manufacturing method thereof.

Background technique In the past, curtains and bedding used in public buildings such as restaurants, hotels, schools, hospitals, etc. are obliged to grant flame retardancy in accordance with the Fire Protection Law to make flame-proof articles. In addition, cushion fabrics, compartment curtains, or window papers have also been recognized as flameproof articles.

In addition, these products cannot be satisfied only with excellent flame retardancy, and further require functional properties such as water repellency, antifouling properties, and bacteriostatic properties. For example, shower curtains used in hotel bathrooms require high water repellency.

In addition, for example, interior materials for vehicles such as car seats must also be provided with flame retardant properties, and for the purpose of imparting antifouling properties, they will be treated with water repellent agents.

According to this, many articles will require both excellent flame retardancy and water repellency, but it is known that most water repellents in the past will significantly reduce the flame retardancy.

As a technique for suppressing the deterioration of flame retardancy caused by water repellent, for example, Patent Document 1 discloses a method that uses flame retardant yarns for fibers to improve flame retardancy, and uses a very small amount of C8 fluorine-based water repellent Used as a water repellent to treat flame retardant yarns. C8 fluorine-based water repellent can impart strong water repellency, so even a small amount of treatment can also impart water repellency. However, in recent years, perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA) contained in C8 fluorine-based water repellent has been pointed out as being toxic to organisms and causing harm to the environment. The C6 fluorine-based water repellent of these compounds, or even a fluorine-free water repellent without fluorine atoms, is used as the water repellent.

However, the water repellent performance of C6 fluorine-based water repellent and non-fluorine water repellent is inferior to C8 fluorine-based water repellent. Therefore, in order to impart sufficient water repellency to fiber products, the amount of use must be increased. On the other hand, as the amount of use increases, the flame retardancy will decrease, so it is difficult to balance excellent flame retardancy and water repellency.

In addition, Patent Document 2 describes that a flame-retardant yarn is used to improve the flame retardancy of fibers, and a small amount of treatment is performed using a wax-based water-repellent agent as a water-repellent agent, thereby achieving both flame retardancy and water repellency. However, it is difficult for wax-based water repellents to impart sufficient water repellency to fibers.

Prior technical literature Patent Literature Patent Document 1: Japanese Patent No. 2944835 Patent Document 2: Japanese Patent Laid-Open No. 2013-155459

Summary of the invention Problems to be solved by invention The main object of the present invention is to provide a water-repellent agent, which can impart excellent water-repellent properties to fibers, and it is not easy to hinder the flame retardancy of fibers. In addition, the present invention also aims to provide a water-repellent fiber product using the water-repellent agent and a manufacturing method thereof.

Means to solve the problem The inventors of the present case have carefully discussed in order to solve the aforementioned problems. As a result, it was found that by dispersing at least an aqueous dispersion of a hydrocarbon compound having a functional group reactive with an isocyanate group and an isocyanate compound in water, and the number of moles of the cross-linkable functional group of the isocyanate compound relative to the aforementioned hydrocarbon compound The molar ratio of the functional groups (mol ratio) is set to a predetermined value, which can impart excellent water repellency to the fiber and effectively suppress the decrease in the flame retardancy of the fiber. The present invention was completed based on these insights through further and repeated discussion.

That is, the present invention provides inventions of the following aspects. Item 1. A water-repellent agent is an aqueous dispersion in which at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group and an isocyanate compound are dispersed in water, and the crosslinkable functional group of the isocyanate compound is relative to the hydrocarbon compound The molar ratio of the functional group is 0.3 or more. Item 2. The water repellent according to Item 1, wherein the hydrocarbon compound having a functional group that can react with an isocyanate group is a compound represented by the following general formula (1): W[-AR] _a [-B] _b (1) [In the general formula (1), W is a (a+b) valent organic group; A is bonded to W and is -XY- or -Y-; B is bonded to W and is -XZ or -Z ; A is an integer of 1 or more; b is an integer of 1 or more; (a+b) is 3 to 8; X is a divalent polyalkylene ether group; Y is a divalent group and is an ether group, an ester group, Acylamino, urethane, urea or thiocarbamate; R is a linear or branched monovalent hydrocarbon group with 6 to 30 carbon atoms that optionally contains at least one unsaturated bond; Z is hydroxyl , Amine, carboxyl or thiol; however, when B is -XZ, Z is hydroxy]. Item 3. The water-repellent agent according to Item 1 or 2, wherein the aforementioned isocyanate compound is a blocked isocyanate. Item 4. The water-repellent agent according to any one of Items 1 to 3, further comprising a surfactant. Item 5. The water-repellent agent according to any one of Items 1 to 4, further comprising an acrylic polymer. Item 6. The water-repellent agent according to Item 5, wherein the content of the acrylic polymer is 0.1 to 99 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound in the water-repellent agent. Item 7. The water repellent agent according to Item 5 or Item 6, wherein the aforementioned acrylic polymer is an acrylic polymer containing a halogen element. Item 8. The water-repellent agent according to any one of Items 5 to 7, wherein the aforementioned acrylic polymer is an acrylic polymer containing no fluorine atom. Item 9. The water repellent according to Item 5 or Item 6, wherein the aforementioned acrylic polymer is an acrylic polymer containing no halogen element. Item 10. The water repellent according to any one of Items 5 to 9, wherein the aforementioned acrylic polymer is an acrylic-polysiloxane polymer. Item 11. A water-repellent fiber product that has been treated with the water-repellent agent according to any one of Items 1 to 10. Item 12. A method for manufacturing a water-repellent fiber product, comprising the step of contacting the water-repellent agent according to any one of Items 1 to 10 with a fiber product. Item 13. A kit comprising: a first agent comprising at least a hydrocarbon compound having a functional group which can react with an isocyanate group; and a second agent comprising at least an isocyanate compound; the aforementioned kit is used to prepare water repellent Agent, the water repellent agent disperses the first agent and the second agent in water to prepare an aqueous dispersion user; the crosslinkable functional group of the isocyanate compound in the second agent is relative to the hydrocarbon in the first agent The molar ratio of the functional group of the compound is 0.3 or more. Item 14. A kit comprising: a first agent comprising at least a hydrocarbon compound having a functional group reactive with an isocyanate group; a second agent comprising at least an isocyanate compound; and a third agent comprising at least acrylic acid polymerization The above set is used to prepare a water repellent agent, which disperses the first agent, the second agent and the third agent in water to make an aqueous dispersion user; the second agent is the isocyanate The molar ratio of the cross-linkable functional group of the compound to the functional group of the hydrocarbon compound in the first agent is 0.3 or more.

Invention effect According to the present invention, a water-repellent agent can be provided, which can impart excellent water-repellent properties to fibers, and it is not easy to hinder the flame retardancy of fibers. In addition, according to the present invention, a water-repellent fiber product using the water-repellent agent and a manufacturing method thereof can also be provided.

Forms for carrying out the invention 1. Water repellent The water repellent of the present invention is characterized in that it is an aqueous dispersion in which a hydrocarbon compound having a functional group reactive with an isocyanate group (hereinafter, sometimes referred to as "isocyanate-reactive hydrocarbon compound") and an isocyanate compound are dispersed in water, The ratio of the number of moles of the crosslinkable functional group of the isocyanate compound to the number of moles of the aforementioned functional group of the hydrocarbon compound (mole ratio) is 0.3 or more. By having such a structure, the water repellent agent of the present invention can impart excellent water repellency to fibers, and can effectively suppress the retardation of fiber flame retardancy. Hereinafter, the water repellent agent of the present invention will be described in detail. In addition, in the following description, a single-liquid water repellent is mainly described. The water repellent is composed of an aqueous dispersion in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are dispersed in water. However, as described later, the present invention It can also be made into the form of the following kit: set as a two-liquid kit, which includes a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound, and when used, the first agent and the aforementioned second agent Disperse in water to prepare an aqueous dispersion to prepare the water repellent of the present invention. In addition, in the present invention, the following kits can also be formed: a three-component kit, which includes a first agent containing an isocyanate-reactive hydrocarbon compound, a second agent containing an isocyanate compound, and a second agent containing an acrylic polymer Three doses. Disperse the first dose, the second dose, and the third dose in water to prepare an aqueous dispersion to prepare the water repellent agent of the present invention.

(Isocyanate-reactive hydrocarbon compound) The hydrocarbon compound having a functional group that can react with an isocyanate group is a hydrocarbon compound that has a functional group that can react with an isocyanate group bonded to a hydrocarbon skeleton. Only one type of isocyanate-reactive hydrocarbon compound may be used, or two or more types may be used in combination. The functional groups that can react with isocyanate groups are preferably exemplified by hydroxyl groups, amine groups, carboxyl groups, and thiol groups.

Examples of the isocyanate-reactive hydrocarbon compound include compounds represented by the following general formula (1). W[-AR] _a [-B] _b (1)

In the general formula (1), W is a (a+b) valent organic group. A is bonded to W and is -X-Y- or -Y-. B is bonded to W and is -X-Z or -Z. a is an integer of 1 or more. b is an integer of 1 or more. (a+b) is 3~8. X is a divalent polyalkylene ether group. Y is a divalent group, and is an ether group, an ester group, an amide group, an urethane group, a urea group, or an thiamine group. R is an optionally linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms containing at least one unsaturated bond. Z is a hydroxyl group, an amine group, a carboxyl group or a thiol group. However, when B is -X-Z, Z is hydroxyl.

In the isocyanate-reactive hydrocarbon compound represented by the general formula (1), the hydroxyl group, amine group, carboxyl group or thiol group of the group Z constitutes a functional group that can react with the isocyanate group. In addition, the isocyanate-reactive hydrocarbon compound is a compound having a hydrocarbon group derived from the group R.

In the isocyanate-reactive hydrocarbon compound of the general formula (1), the group W is an (a+b)-valent organic group, and it is preferably a residue of a polyfunctional compound. A group A and a group B are bonded to the group W. a is an integer of 1 or more, b is an integer of 1 or more, and (a+b) is 3-8. That is, the valence of the base W is 3-8. Multifunctional compounds are preferably exemplified by polyol compounds, polyamine compounds, polycarboxylic acid compounds, and polythiol compounds.

The polyol compound is not limited, and for example, it can be selected from trimethylolethane, trimethylolpropane, ditrimethylolpropane, 1,2,4-butanetriol, glycerin, and sugar alcohol. The sugar alcohol is not limited, and examples include compounds derived from aldose and ketose, such as butanose, pentose, hexose, and heptose. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose Sugar, fructose, ribulose, mannoheptulose, sedum heptulose, threose, erythritol, threitol, glucopyranose, pyranulose, pyranallose, pyranallose Sugar, apraranose, idylpyranose, glucopyranose, glucose alcohol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, seaweed Sugar alcohol, iditol, inositol, neopentaerythritol, dipentaerythritol, heptacosanol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, gluconolactone, glyceric acid Lactone, xylulactone, glucosamine, galactosamine or a mixture of these.

The polyamine compound is not limited, and examples thereof include diethylenetriamine, triethylenetetramine, amineethylethanolamine, diethanolamine, and triethanolamine.

The polycarboxylic acid compound is not limited, and examples include malic acid and citric acid.

The polythiol compound is not limited, and examples include trimethylolpropane ginseng (3-mercaptopropionate), ginseng-[(3-mercaptopropionyloxy)-ethyl]-trimer isocyanate, neopentyl Tetral alcohol (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), etc.

In A and B of the general formula (1), the group X is a divalent polyalkylene ether group (that is, polyoxyalkylene group). Specific examples of the radical X include, for example, homopolymers such as oxyethylidene oxide, oxypropylene oxide, and oxybutylene oxide, and block copolymers and random copolymers obtained by combining two or more of these.

As described above, the group Y is a divalent group, and is an ether group, an ester group, an amide group, an urethane group, a urea group, or an thiamine group.

The group R is bonded to the group Y, and is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms and optionally containing at least one unsaturated bond. The lower limit of the carbon number of the hydrocarbon group is preferably 8 or more, more preferably 10 or more, more preferably 12 or more, and the upper limit is preferably 28 or less, more preferably 26 or less, more preferably 24 or less, and the ideal range may be For example: 6~28, 6~26, 6~24, 8~30, 8~28, 8~26, 8~24, 10~30, 10~28, 10~26, 10~24, 12~30 , 12~28, 12~26, 12~24, especially ideal is 12~24. Specific examples of the hydrocarbon group include: decyl, undecyl, dodecyl (lauryl), fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, and twenty , 21 base, 22 base, oil base, etc.

In the method of introducing the group R in the general formula (1), a higher fatty acid (in addition, the aforementioned carbon number also includes the carbon number of the carbonyl group), a higher aliphatic alcohol, a higher aliphatic monoisocyanate, a higher aliphatic amine, a halogenated alkane A method of reacting a hydroxyl group, fatty acetyl chloride, etc. with the hydroxyl group, carboxyl group, thiol group, amine group, etc. of the aforementioned multifunctional compound. Thereby, the bond between the group Y and the group R can be formed, and the group R can be introduced into the general formula (1).

Examples of higher fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, tetracosanoic acid, palmitic oleic acid, linoleic acid, arachidic acid, Oleic acid, erucic acid, etc.

Examples of higher aliphatic alcohols include lauryl alcohol, tridecanol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, twenty-one alcohol, behenyl alcohol, and oleyl alcohol.

Examples of the higher aliphatic monoisocyanate include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, and diisocyanate. Decayl isocyanate, behenyl isocyanate, etc.

Examples of higher aliphatic amines include decylamine, laurylamine, myristylamine, stearylamine, behenylamine, and oleylamine.

Examples of the halogenated alkyl group include chlorododecane, chlorohexadecane, chlorooctadecane, bromododecane, bromohexadecane, and bromooctadecane.

Examples of fatty acid chlorides include octyl chloride, decyl chloride, laurel chloride, nutmeg chloride, palmitic chloride, stearyl chloride, oleoyl chloride, and the like.

The isocyanate-reactive hydrocarbon compound is preferably at least one selected from the group consisting of the above-mentioned polyfunctional compound and the above-mentioned higher fatty acid, higher aliphatic alcohol, higher aliphatic monoisocyanate, higher aliphatic amine, halogenated alkyl group and fatty acetyl chloride One type of reaction product. The reaction product has a hydrocarbon skeleton derived from the aforementioned polyfunctional compound, and has a functional group (preferably a hydroxyl group, an amine group, a carboxyl group, or a thiol group) that can react with an isocyanate group.

In the isocyanate-reactive hydrocarbon compound, the lower limit of the number of functional groups that can react with the isocyanate group in one molecule is preferably 1 or more, the upper limit is preferably 7 or less, more preferably 5 or less, more preferably 3 or less, and the range is preferably 1 ~7, ideally 1~5, more ideally 1~3.

(Isocyanate compound) In addition, as the isocyanate compound, a known isocyanate compound (multifunctional isocyanate compound) having two or more crosslinkable functional groups in one molecule can be used alone or in combination of two or more. In addition, in the present invention, the crosslinkable functional group of the isocyanate compound is specifically an isocyanate group or a blocked isocyanate group. Accordingly, in the water repellent of the present invention, the total molar ratio of the isocyanate group and the blocked isocyanate group of the isocyanate compound to the functional group of the hydrocarbon compound is 0.3 or more.

In addition, as the isocyanate compound, the following blocked isocyanate can be suitably used: 50 mol% or more of the isocyanate group, preferably 60 mol% or more, and more preferably 70 mol% or more, which has been blocked with a blocking agent. As the blocked isocyanate, various known blocked isocyanates can be used. The blocked isocyanate can be prepared by reacting various known blocking isocyanate compounds with various known blocking agents.

The isocyanate compound (including blocked isocyanate) may also have self-emulsifying properties. For example, the isocyanate compound having self-emulsifying properties may use an isocyanate compound that has introduced a nonionic hydrophilic group, a cationic hydrophilic group, and an anionic hydrophilic group into a part of the isocyanate compound From the viewpoint of water repellency, it is desirable to use an isocyanate compound into which a nonionic hydrophilic group having an oxyethyl group has been introduced. Examples of the hydrophilic compound that reacts with the isocyanate compound to impart self-emulsification include polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol polypropylene glycol monomethyl ether, and polypropylene glycol poly Polyoxyalkylene monoalkyl ethers such as ethylene glycol monobutyl ether; (poly)ethylene glycols such as ethylene glycol or diethylene glycol, triethylene glycol, polyethylene glycol; polyethylene glycol , Block copolymers, random copolymers of polypropylene glycol and butylene glycol, random copolymers or block copolymers of ethylene oxide and propylene oxide, ethylene oxide and butylene oxide; polyoxy Alkylene monoamines, polyoxyalkylene diamines, etc.; polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, etc. are preferably used. The nonionic hydrophilic compound may be used alone or in combination of two or more. By introducing a predetermined amount of these compounds into the isocyanate group, the isocyanate compound can be given self-emulsifying properties. With respect to the isocyanate group, the lower limit of the introduction amount of these compounds is preferably 1 mol% or more, and the upper limit is preferably 50 mol% or less, more preferably 40 mol% or less, more preferably 30 mol% or less, and the range is preferably 1 to 50 mol %, more preferably 1~40mol%, more ideally 1~30mol%.

Examples of the isocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate. Examples of aliphatic polyisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 2,2,4-trimethyl Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, ionic acid diisocyanate, dimer acid diisocyanate, etc.; cycloaliphatic polyisocyanate, for example, 1,3- Bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane Alkane (isophorone diisocyanate), bis-(4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, etc.; examples of aromatic polyisocyanates include 2,4'-diphenyl Methane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthalene diisocyanate Etc.; aromatic aliphatic polyisocyanates include, for example, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, α,α,α',α'-tetramethylxylene diisocyanate, etc.; Use isocyanate reactions using reactions of these compounds, such as addition polyisocyanate, or uretdioneation reaction, trimerization isocyanation reaction, carbodiimide reaction, uretonization reaction, biuretization reaction, etc. Plastids and mixtures of these.

The blocking agent introduced into the isocyanate compound is a compound having one or more active hydrogens in the molecule, and can be used alone or in combination of two or more. Examples of the blocking agent include alcohol-based compounds, alkylphenol-based compounds, phenol-based compounds, active methylene-based compounds, thiol-based compounds, amide-based compounds, amide-based compounds, imidazole-based compounds, imidazoline Compound, triazole compound, carbamic acid compound, urea compound, oxime compound, amine compound, amide imine compound, imine compound, pyrazole compound, bisulfite, etc. Among them, amide-based compounds, active methylene-based compounds, oxime-based compounds, and pyrazole-based compounds are preferred, and ε-caprolactam, acetone, diethyl malonate, and methyl ethyl are preferred Ketone oxime, cyclohexanone oxime, 3-methylpyrazole, 3,5-dimethylpyrazole, etc.

In the water repellent of the present invention, the ratio of the number of moles of the cross-linkable functional group of the isocyanate compound to the number of moles of the functional group of the isocyanate-reactive hydrocarbon compound (mole ratio) may be 0.3 or more. From the viewpoint of appropriately imparting excellent water repellency to fibers and effectively inhibiting the flame retardancy of fibers, the lower limit of the molar ratio is preferably 0.4 or more, more preferably 0.5 or more, and the upper limit is preferably 8 or less, more preferably 6 The following, more ideal is 4 or less, the ideal range is preferably 0.3~8, 0.3~6, 0.3~4, 0.4~8, 0.4~6, 0.4~4, 0.5~8, 0.5~6, 0.5~4, Especially ideal is 0.5~4.

In the water repellent of the present invention, the mass ratio of the isocyanate-reactive hydrocarbon compound to the isocyanate compound (isocyanate-reactive hydrocarbon compound: isocyanate compound) is not limited, as long as the fiber is appropriately given excellent water repellency and the fiber resistance is effectively suppressed From the standpoint of flammability, it is preferably 1:0.001~1000, more preferably 1:0.05~20, and even more preferably 1:0.1~10.

The water repellent of the present invention can be a processing fluid that directly treats the concentration of the fiber product, or it can be a stock solution that is diluted with water before being used in the treatment of the fiber product (for example, the stock solution is diluted to 5 to 1000 times to make the processing Liquid use).

When the water repellent of the present invention is used as a stock solution, the lower limit of the content (solid content) of the isocyanate-reactive hydrocarbon compound is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass or less. The ideal range can be exemplified by: 0.01-60% by mass, 0.01-50% by mass, 0.01-40% by mass , 0.5-60% by mass, 0.5-50% by mass, 0.5-40% by mass, 1.0-60% by mass, 1.0-50% by mass, 1.0-40% by mass, particularly preferably 1.0-40% by mass.

Similarly, when the water repellent of the present invention is used as a stock solution, the lower limit of the content (solid content) of the isocyanate compound is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass or less. The ideal range can be exemplified by: 0.01-60% by mass, 0.01-50% by mass, 0.01-40% by mass , 0.5-60% by mass, 0.5-50% by mass, 0.5-40% by mass, 1.0-60% by mass, 1.0-50% by mass, 1.0-40% by mass, particularly preferably 1.0-40% by mass.

In the water repellent of the present invention, the isocyanate-reactive hydrocarbon compound and the isocyanate compound need only be an aqueous dispersion dispersed in water. More specifically, the water repellent of the present invention may be, for example, an aqueous dispersion in which particles of isocyanate-reactive hydrocarbon compounds and particles of isocyanate compounds are dispersed in water, or may contain isocyanate-reactive hydrocarbon compounds and isocyanate compounds in one particle Aqueous dispersion of particles. The water-based dispersion in which the particles of the isocyanate-reactive hydrocarbon compound and the particles of the isocyanate compound are dispersed in water can be easily prepared by mixing the water-based dispersion of the isocyanate-reactive hydrocarbon compound and the water-based dispersion of the isocyanate compound. In addition, an aqueous dispersion containing particles of an isocyanate-reactive hydrocarbon compound and an isocyanate compound in one particle can also be prepared by mixing an isocyanate-reactive hydrocarbon compound and an isocyanate compound and then performing aqueous dispersion.

The water repellent of the present invention may contain other components in addition to the isocyanate-reactive hydrocarbon compound, isocyanate compound and water. Other ingredients should be exemplified by acrylic polymers, surfactants, flame retardants, polysiloxanes, other additives, etc. As for other components, only one type may be used, or two or more types may be used in combination. However, the water-repellent agent of the present invention preferably does not contain a C8 fluorine-based water-repellent agent (a compound having a perfluoroalkyl group having 8 or more carbon atoms).

In addition, for example, the acrylic polymer can be appropriately prepared into an aqueous dispersion, so it can be blended even when the water repellent of the present invention is a stock solution, and the water repellent of the present invention is diluted with water to make a processing liquid It can also be blended with water when preparing the processing fluid. Further, regarding the surfactant, when the water-repellent agent of the present invention is used as an aqueous dispersion, an isocyanate-reactive hydrocarbon compound or an isocyanate compound can be suitably used to disperse in water. Therefore, the water-repellent agent of the present invention is a stock solution It should also be blended. The time when other ingredients are added to the water-repellent agent may be appropriately selected. Hereinafter, other components will be described in detail.

(Acrylic polymer) From the viewpoint of water repellency and flame retardancy, the water repellent agent of the present invention may also contain an acrylic polymer if necessary. Only one type of acrylic polymer may be used, or two or more types may be used in combination.

The acrylic polymer can use a well-known thing as an aqueous dispersion. For example, from the viewpoint of imparting more excellent water repellency to fibers, a fluorine atom-containing acrylic polymer is preferred. Moreover, from the viewpoint of obtaining excellent flame retardancy of fibers, an acrylic polymer containing chlorine atoms is preferred. In addition, from the viewpoint of environmental concerns, it is also appropriate to use acrylic polymers that do not contain halogen elements.

The acrylic polymer is a polymer obtained by polymerizing at least (meth)acrylate monomers. As described later, by copolymerizing a halogen atom-containing monomer and a (meth)acrylate monomer, a halogen atom-containing acrylic polymer can be produced.

The (meth)acrylate monomer preferably has an ester moiety having 12 or more carbon atoms, and the ester moiety is preferably a hydrocarbon group other than the ester group. The hydrocarbon group may be linear or branched, may be a saturated hydrocarbon or an unsaturated hydrocarbon, and may have an alicyclic or aromatic ring. Among these, the linear form is preferred, and the linear alkyl form is more preferred.

From the viewpoint of improving water repellency, the carbon number of the ester part is preferably 12 or more, and preferably 30 or less, more preferably 12-30. The carbon number of the ester part is more preferably 21 or less, and preferably 12 to 21. When the carbon number is within this range, the water repellency and tactile sensation become particularly excellent. A linear alkyl group having 12 to 18 carbon atoms is particularly preferable as the ester moiety.

Examples of (meth)acrylate monomers include lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (meth) Base) behenyl acrylate, etc., one or more of these can be used.

Examples of (meth)acrylate monomers having a cyclic structure in the ester portion include benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and (methyl) )Phenoxyethyl acrylate, naphthyl (meth)acrylate, 4-morpholinoethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentyl (meth)acrylate , Dicyclopentenyloxyethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, glycidyl (meth)acrylate, etc., one of these or Plural kinds.

Moreover, the (meth)acrylate monomer preferably contains a functional group having crosslinkability. The functional group may be exemplified by hydroxyl group, epoxy group, chloromethyl group, blocked isocyanate group, amine group, carboxyl group, etc. Specifically, it may be exemplified by diacetone (meth)acrylamide, N-methylol group (Meth)acrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetylacetoxy Ethyl (meth)acrylate, vinyl monochloroacetate, glycidyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (methyl) Acrylic esters, etc. One or more of these can be used.

The (meth)acrylate monomer may, for example, be a radical reactive organic polysiloxane macromonomer. In the acrylic polymer, if the radical reactive organic polysiloxane macromonomer is copolymerized, the acrylic polymer will constitute an acrylic-polysiloxane polymer.

The radical reactive organic polysiloxane macromonomer can have one or more radical reactive groups in one molecule, especially one is preferred. Examples of the radical reactive group include azo group, mercapto group, vinyl group, styryl group, (meth)acryloyl group, etc. At least one of them can be used. From the standpoint of the ease of radical copolymerization, the ease of synthesis, or the ease of obtaining commercial products, the reactive group is preferably a (meth)acryloyl group. Such radically reactive organic polysiloxane macromonomers can be selected from commercially available products. For example, X-22-174ASX, X-22-174BX, X-22-2426, KF-2012, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. may be used.

In addition, other monomers that can be copolymerized with the (meth)acrylate monomer include, for example, other polymerizable monomers other than the (meth)acrylate monomer, or organic polymerization with a radical-reactive group Siloxane is different from other giant monomers. Examples of other monomers include styrene, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ether, acrylonitrile, alkanol acrylamide, maleic diester, (methyl) Acrylic acid methoxy polyalkylene glycol etc. Other monomers are not limited to these examples.

For example, by copolymerizing vinyl chloride or vinylidene chloride with (meth)acrylate monomers, an acrylic polymer containing chlorine atoms can be prepared. Similarly, for example, by copolymerizing a fluorine-containing monomer having a perfluoroalkyl group and an ethylenically unsaturated double bond with a (meth)acrylate monomer, a fluorine atom-containing acrylic polymer can be prepared. In the fluorine-containing monomer, the carbon number of the perfluoroalkyl group is preferably 1 or more, and preferably 6 or less, and ideally 1 to 6.

As the acrylic polymer, for example, Japanese Patent No. 5572385, Japanese Patent No. 5585078, Japanese Patent No. 5678660, Japanese Patent Table 2017-534713, Japanese Patent Table 2017-536439, Japanese Patent Table 2017-538793, Japanese Patent No. 4927760, Japanese Patent No. 5397823, Japanese Patent No. 5500238, Japanese Patent No. 5626337, Japanese Patent No. 6015003, Japanese Patent No. 6249048, Japan Those described in Patent No. 6280298, Japanese Patent No. 4986875, etc.

The acrylic polymer may be an acrylic polymer containing halogen atoms or an acrylic polymer not containing halogen atoms. As described above, for example, from the viewpoint of imparting more excellent water repellency to the fiber, an acrylic polymer containing a fluorine atom is preferred. Moreover, from the viewpoint of obtaining excellent flame retardancy of fibers, an acrylic polymer containing chlorine atoms is preferred. In addition, from the viewpoint of environmental concerns, it is also preferable to use an acrylic polymer that does not contain halogen elements such as fluorine atoms or chlorine atoms.

In addition, the acrylic polymer can be suitably prepared as an aqueous dispersion by, for example, emulsion polymerization. Therefore, by mixing the isocyanate-reactive hydrocarbon compound and the isocyanate compound prepared into the aqueous dispersion, and the acrylic polymer prepared into the aqueous dispersion, the water repellent agent can be easily prepared.

When the water-repellent agent of the present invention contains an acrylic polymer, the lower limit of the content of the acrylic polymer relative to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more. It is preferably 1.0 part by mass or more, and the upper limit is preferably 99 parts by mass or less, more preferably 55 parts by mass or less, more preferably 35 parts by mass or less, and the ideal range is 0.1 to 99 parts by mass, 0.1 to 55 parts by mass Parts, 0.1 to 35 parts by mass, 0.5 to 99 parts by mass, 0.5 to 55 parts by mass, 0.5 to 35 parts by mass, 1.0 to 99 parts by mass, 1.0 to 55 parts by mass, 1.0 to 35 parts by mass, particularly preferably 1.0 to 35 parts by mass.

(Surfactant) As the surfactant, one or a plurality of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene Ethyl sorbitan fatty acid ester, polyoxyethyl sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethyl glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxygenated Ethyl alkyl amine, polyoxyethylene fatty acid amide, fatty acid alkanol amide, alkyl alkanol amide, acetylene glycol, ethylene oxide adduct of acetylene glycol, polyethylene glycol poly Propylene glycol block copolymer, etc.

Examples of anionic surfactants include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, and polyoxyethyl esters. Alkyl phenyl ether sulfate, vinyl sulfosuccinate, etc.

Examples of the cationic surfactants include amine salts, amidoamine salts, quaternary ammonium salts, and imidazolinium salts. Specific examples are not particularly limited, and examples include alkylamine salts, polyoxyethylidene alkylamine salts, alkylamidoamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc. Amine salt type surfactant, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl pyridinium salt, alkyl isoquinolinium salt, chloride Bensonin and other quaternary ammonium salt surfactants.

Amphoteric surfactants can be exemplified by alkylamine oxides, anilines, imidazolinium betaines, amide betaines, betaines acetate, etc. Specifically, for example, long-chain amine oxides, lauryl Betaine, octadecyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetate betaine, fatty acid amidopropyl dimethylamino acetate betaine, etc.

When the water repellent of the present invention contains a surfactant, the content of the surfactant is 100 parts by mass relative to the solid content of the water repellent, and the lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more ideal It is 1.5 parts by mass or more, and the upper limit is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. The ideal range can be exemplified by: 0.5 to 30 parts by mass, 0.5 to 20 parts by mass, 0.5 to 10 parts by mass, 1 to 30 parts by mass, 1 to 20 parts by mass, 1 to 10 parts by mass, 1.5 to 30 parts by mass, 1.5 to 20 parts by mass, 1.5 to 10 parts by mass, particularly ideal 1.5~10 parts by mass.

(Flame retardant) From the viewpoint of further improving the flame retardancy of the fiber, the water repellent of the present invention can be further blended with a flame retardant. The flame retardant is not particularly limited, for example, known flame retardants such as bromine flame retardants, phosphorus flame retardants, nitrogen flame retardants, metal salt flame retardants, silicon flame retardants, inorganic flame retardants, etc. can be used. Fuel. In addition, as will be described later, the fiber products to which the water-repellent agent of the present invention is treated may be subjected to flame retardant treatment in advance, and such flame retardants may be used in the flame retardant treatment.

When the flame retardant is used in combination with the water repellent of the present invention, the lower limit of the content (solid content) of the flame retardant in the processing liquid is preferably 1% by mass or more, the upper limit is preferably 40% by mass or less, and more preferably 30% by mass The following is more preferably 25% by mass or less, and the range can be listed as follows: ideally 1-40% by mass, more preferably 1-30% by mass, and even more preferably 1-25% by mass.

(Polysiloxane) One or more kinds of polysiloxane compounds can be used in the water repellent of the present invention.

For the polysiloxane compound, for example, amine-modified polysiloxane can be used. Amino-modified polysiloxone can use those that have introduced amine groups to the side chain of the siloxane structure, those that have introduced amine groups to the end of the siloxane structure, or any of these mixtures. The amine groups can be used Monoamine, diamine or partially blocked. In amine-modified polysiloxane, from the viewpoint of water repellency, the amine equivalent is preferably 300g/mol or more, and preferably 20,000g/mol or less, more preferably 300~20000g/mol, when considering fiber products In terms of water repellency, washing durability, touch and price, etc., it is more preferably 1000 g/mol or more, and more preferably 7000 g/mol or less, and particularly preferably 1000 to 7000 g/mol. Such amine-modified polysilicone can be used as a commercial product. For example, WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 manufactured by Wacker Asahikasei Silicone Co., Ltd., KF-867, KF-869, and KF-8004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Also, methanol can be used to modify polysiloxane. The methanol-modified polysiloxane can use any one that has introduced a hydroxyl group into the side chain of the siloxane structure, a hydroxy group introduced into the end of the siloxane structure, or a mixture of these. Such methanol-modified polysilicone can be used as a commercial product. For example, X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003 can be used manufactured by Shin-Etsu Chemical Industry Co., Ltd. Wait.

In addition, diol modified polysiloxane can also be used. The diol-modified polysiloxane can use any of those in which a diol group has been introduced into the side chain of the siloxane structure, a diol group has been introduced into the end of the siloxane structure, or a mixture of these. Such diol-modified polysiloxane can be selected from commercially available products. For example, X-22-176DX, X-22-176F, X-22-176GX-A, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. may be used.

In addition, phenol-modified polysiloxane can also be used. For the phenol-modified polysiloxane, any one of phenolic hydroxyl group introduced into the side chain of the siloxane structure, phenolic hydroxyl group introduced into the end of the siloxane structure, or a mixture of these may be used. This kind of phenol-modified polysiloxane can be selected from commercially available products. For example, KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

In addition, carboxyl modified polysiloxane can also be used. The carboxyl-modified polysiloxane can use any one that has introduced a carboxyl group to the side chain of the siloxane structure, a carboxyl group that has been introduced to the end of the siloxane structure, or a mixture of these. Such carboxyl-modified polysiloxane can be selected from commercially available products. For example, X-22-3701E, X-22-162C, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. can be used.

Alternatively, mercapto-modified polysiloxane can also be used. The mercapto-modified polysiloxone may use any one that has introduced a mercapto group into the side chain of the siloxane structure, a mercapto group that has been introduced into the end of the siloxane structure, or a mixture of these. Such mercapto-modified polysilicone can be used as a commercial product. For example, KF-2001, KF-2004, X-22-167B, X-22-167C, etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd. may be used.

Alternatively, epoxy-modified polysiloxane can also be used. The epoxy-modified polysiloxane can be any one of which has introduced an epoxy group into the side chain of the siloxane structure, an epoxy group has been introduced into the end of the siloxane structure, or a mixture of these. This epoxy-modified polysiloxane can be selected from commercially available products. For example, X-22-343, KF-101, KF-1001, X-22-163, X-22-163A, X-22-163B, X-22-163C, KF manufactured by Shin-Etsu Chemical Industry Co., Ltd. can be used -105, X-22-169AS, X-22-169B, X-22-173BX, X-22-173DX, etc.

In addition, fluoroalkyl modified polysiloxane can also be used. The fluoroalkyl modified polysiloxane can be selected from commercially available products. For example, Fluorosil J15, Fluorosil D2, Fluorosil H418, and Fluorosil L118 manufactured by SILTECH can be used.

In addition, long-chain alkyl modified polysiloxane can also be used. Long-chain alkyl modified polysiloxane can be selected from commercial products, for example, KF-412, KF-413, KF-414, KF-415, KF-4003, KF manufactured by Shin-Etsu Chemical Co., Ltd. -4701, KF-4917, KF-7235B, X-22-7322, Asahi Kasei Wacker Asahikasei Silicone (Wacker Asahikasei Silicone) company made BELSIL CDM 3526 VP, BELSIL CM 7026 VP, BELSIL SDM 5055 VP, etc.

In addition, long-chain alkyl-aralkyl modified polysiloxane can also be used. The long-chain alkyl-aralkyl modified polysiloxane can be selected from commercially available products. For example, X-22-1877 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

In addition, long-chain alkyl-polyether modified polysiloxane can also be used. The long-chain alkyl-polyether modified polysiloxane can be selected from commercially available products. For example, Silube T308-16, Silube T310-A16, Silube J208-812 manufactured by SILTECH can be used.

In addition, the higher fatty acid amide can be used to modify polysiloxane. The modified high-grade fatty acid amide polysiloxane can be selected from commercially available products. For example, KF-3935 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

In addition, dimethyl polysiloxane or methylphenyl polysiloxane can also be used. Dimethyl polysiloxane or methyl phenyl polysiloxane can be selected from commercially available products. For example, if it is dimethyl polysiloxane, KF-96, KF-965, KF-968, KF-995, etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be used; if it is methyl phenyl polysiloxane, then KF-50, KF-54, KF-56, etc. are manufactured using Shin-Etsu Chemical Industry Co., Ltd.

Alternatively, silanol-terminated polysiloxane can also be used. Silanol-terminated polysiloxane can be selected from commercially available products. For example, Shin-Etsu Chemical Co., Ltd. X-21-5841, KF-9701, etc. can be used.

In addition, from the viewpoint of imparting anti-slip properties, a polysiloxane resin compound may also be used. Polysiloxane resins can use well-known substances. For example, it is preferable to use an organic polysiloxane composed of MQ, MDQ, MT, MTQ, MDT, or MDTQ in a solid shape at 25°C and having a three-dimensional structure. . Here, M, D, T, and Q represent (R') ₃ SiO _0.5 unit, (R') ₂ SiO unit, R'SiO _1.5 unit, and SiO ₂ unit, respectively. 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. Silicone resins are generally known as MQ resins, MT resins or MDT resins, and sometimes have portions indicated as MDQ, MTQ or MDTQ.

Silicone resin can also be obtained by making a solution, that is, dissolving it in a suitable solvent. Examples of the solvent include: lower molecular weight methyl polysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropanol, methylene chloride, 1,1 , 1-Trichloroethane and mixtures of these solvents.

This kind of polysiloxane resin can be selected from commercially available products. For the solution, for example, KF-7312J, KF-7312K, KF-7312L, KF-7312T, KF-9021L manufactured by Shin-Etsu Chemical Co., Ltd. can be used. For silicone resin alone, for example, KR-220L, KR-216 manufactured by Shin-Etsu Chemical Co., Ltd., DOWSIL MQ-1600 Solid Resin manufactured by Dow Corning Toray Co., Ltd., DOWSIL MQ-1640 Flake Resin, Asahi Kasei Wacker Poly Silicone (Wacker Asahikasei Silicone) company manufactures SILRES MK POWDER, SILRES MK FLAKE, SILRES 604 and so on.

Moreover, a well-known silane coupling agent can also be used. Examples of the silane coupling agent include silane coupling agents containing epoxy groups, amine groups, mercapto groups, and isocyanate groups. Such silane coupling agent can be selected from commercially available products. For example, the silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. The silane coupling agent containing epoxy groups can use KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, etc. The silane coupling agent can use KBM-602, KBM-608, KBM-903, KBE-903, KBM-573, etc., the silane coupling agent containing mercapto group can use KBM-802, KBM-803, etc., containing isocyanate group silane coupling The agent can use KBE-9007 and so on.

When the water-repellent agent of the present invention contains a polysiloxane compound, the content of the polysiloxane compound is 100 parts by mass relative to the total of the hydrocarbon compound and the isocyanate compound, the lower limit is preferably 0.01 part by mass or more, and the upper limit is preferably 100 parts by mass or less. It is preferably 70 parts by mass or less, more preferably 45 parts by mass or less. The range can be listed as follows: ideally 0.01 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, more preferably 0.01 to 45 parts Quality parts.

(Other additives) The water-repellent agent of the present invention may contain any additives in addition to the other components mentioned above as long as it can produce the effects of the present invention. Examples of additives include various sorbitan derivatives described in International Publication No. 2014/190905, alkyl citrate derivatives, and fatty acid esters such as neopentyl alcohol derivatives, and U.S. Publication No. 2010/0190397 The described hydrophobic compound or the hydrophobic compound described in Japanese Patent Laid-Open No. 2017-222827, a wax-based compound, a water-repellent auxiliary component, a crosslinking agent (a compound different from the isocyanate compound), an anti-slip agent, an anti-wrinkle agent, Known additives such as flame retardants, antistatic agents, heat-resistant agents and other fiber agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, hardening accelerators, deodorants, antibacterial agents and the like. For example, the water-repellent adjuvant component may be a zirconium-based compound, etc., particularly preferably zirconium acetate, zirconium hydrochloride, and zirconium nitrate. These additives can be used alone or in combination of two or more.

In the water repellent of the present invention, the isocyanate-reactive hydrocarbon compound and the isocyanate compound need only be an aqueous dispersion dispersed in water. As described above, the water-based dispersion in which the particles of the isocyanate-reactive hydrocarbon compound and the particles of the isocyanate compound are dispersed in water It can be easily produced by mixing an aqueous dispersion of an isocyanate-reactive hydrocarbon compound and an aqueous dispersion of an isocyanate compound. In addition, after mixing an aqueous dispersion of an acrylic polymer, a water repellent further containing an acrylic polymer can be easily produced. An aqueous dispersion containing particles of isocyanate-reactive hydrocarbon compound and isocyanate compound in one particle can be produced by generating the isocyanate-reactive hydrocarbon compound and isocyanate compound in the same water.

In the present invention, various aqueous dispersions can be produced by a known method, for example, a method of adding water to disperse after mixing various components and a surfactant, or a method of mechanically dispersing using a known disperser or the like . The dispersing machine can use a homogenizing mixer, a homogenizing machine, a colloid mill, a pipeline mixer, a sand mill, etc. In addition, when dispersing the water system, a known organic solvent may be added.

As mentioned above, the present invention can also be made into the form of a kit: set as a two-liquid kit, which includes a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound. When used, the first agent And the aforementioned second agent is dispersed in water to prepare an aqueous dispersion to prepare the water repellent agent of the present invention. In addition, in the present invention, the following kits can also be formed: a three-component kit, which includes a first agent containing an isocyanate-reactive hydrocarbon compound, a second agent containing an isocyanate compound, and a second agent containing an acrylic polymer Three doses. Disperse the first dose, the second dose, and the third dose in water to prepare an aqueous dispersion to prepare the water repellent agent of the present invention.

Specifically, the two-component kit of the present invention includes: a first agent, which contains at least a hydrocarbon compound having a functional group that can react with an isocyanate group; and a second agent, which contains at least an isocyanate compound; The water-repellent agent is prepared by dispersing the first agent and the second agent in water to make an aqueous dispersion user; the cross-linkable functional group of the isocyanate compound in the second agent relative to the hydrocarbon compound in the first agent The molar ratio of the functional group is 0.3 or more.

Furthermore, the three-component kit of the present invention includes: a first agent, which contains at least a hydrocarbon compound having a functional group reactive with an isocyanate group; a second agent, which contains at least an isocyanate compound; and a third agent, which contains at least Acrylic polymer; the aforementioned set is used to prepare a water repellent agent, which disperses the first agent, the second agent and the third agent in water to make an aqueous dispersion user; the intersection of the isocyanate compound in the second agent The molar ratio of the linked functional group to the functional group of the hydrocarbon compound in the first agent is 0.3 or more.

The two-liquid kit and three-liquid kit of the present invention are used to prepare the water repellent of the present invention. Therefore, the types and contents of isocyanate-reactive hydrocarbon compounds, isocyanate compounds, acrylic polymers, and other components are also the same as the water repellent of the present invention. In addition, for example, in the case of a two-component kit, at least one of the acrylic polymer and other components may be blended into the first agent and the second agent. In addition, for example, in the case of a three-component kit, other components may be blended in at least one of the first agent, the second agent, and the third agent.

2. Water-repellent fiber products The water-repellent fiber product of the present invention is treated with the aforementioned water-repellent agent of the present invention. That is, the water-repellent fiber product of the present invention is manufactured by bringing the water-repellent agent of the present invention into contact with the fiber product. The details of the water repellent of the present invention are as described above.

The fiber products treated with the water repellent of the present invention are not particularly limited as long as they are made of fibers, and examples include natural fibers such as cotton, silk, hemp, wool, polyester, nylon, and acrylic , Elastic fibers and other synthetic fibers and fiber products using these. In addition, the shape and shape of fiber products are not limited, and are not limited to the shape of raw materials such as velvet, silk, rattan, yarn, etc., but can also be woven fabrics, woven fabrics, fillings, non-woven fabrics, paper, sheets, films, etc Various processing forms.

In addition, flame retardant treatment may be applied to fiber products in advance. For example, in the case of polyester, compatibility with spinning properties and the like may be considered, and the flame retardant treatment may be appropriately selected from the aforementioned flame retardants. In addition, the treatment method using the flame retardant is not particularly limited, and it can be mixed in by simply adding it to the polymer, or by copolymerizing it with polyester at the molecular level.

The water repellent agent of the present invention can be used to perform water repellent treatment on fiber products (cloth, etc.) by a known method. The processing method of the fiber product using the water repellent of the present invention may, for example, be a continuous method or a batch method. In addition, when the water repellent of the present invention is a stock solution, in order to form a concentration suitable for processing (for example, the solid content concentration is 0.01% by mass or more, or 6% by mass or less, preferably 0.01 to 6% by mass), The liquid agent is diluted with water to prepare a processing liquid.

In the continuous method, when preparing the processing liquid, in addition to water, it is also appropriate to add various chemicals, such as a cross-linking agent. Next, the object to be treated (that is, the fiber product) is continuously fed into the impregnation device that has been filled with the processing liquid, and after the object is immersed in the processing liquid, the unnecessary processing liquid is removed. The impregnation device is not particularly limited, and a dip dyeing machine, a touch roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator, etc. can be used as appropriate, especially for dip dyeing Machine style is better. Next, using a dryer, an operation to remove water remaining on the object is performed. There are no special restrictions on the dryer, it is suitable for hot air, stenter and other cloth spreading dryer. This continuous method is suitable when the object to be treated is a cloth or the like.

In addition, the batch method consists of the following steps: immersing the object to be processed in the processing liquid; and removing water remaining on the object to be processed. This batch method is suitable for the following situations: when the object to be treated is not cloth-like, such as loose wool, wool tops, slivers, skeins, rattan, yarn, etc., or knitted fabrics are not suitable for the continuous method Situation. In the dipping step, for example, a raw cotton dyeing machine, a yarn dyeing machine, a flow dyeing machine, an industrial washing machine, a beam dyeing machine, and the like can be used. In the operation of removing water, a warm air dryer such as a cone dryer, a beam dryer, a drum dryer, or a high-frequency dryer can be used. The object to which the water repellent of the present invention is attached is preferably subjected to dry heat treatment.

The lower limit of the temperature for dry heat treatment is preferably 120°C or more, and more preferably 160°C or more, and the upper limit is preferably 180°C or less, and the range is preferably 120 to 180°C, especially 160 to 180°C. The lower limit of the dry heat treatment time is preferably 10 seconds or more, more preferably 1 minute or more, and the upper limit is preferably 3 minutes or less, more preferably 2 minutes or less, and the ideal range can be exemplified as: 10 seconds to 3 minutes , 10 seconds to 2 minutes, 1 to 3 minutes, 1 to 2 minutes. The method of dry heat treatment is not particularly limited. When the object to be treated is cloth-like, it is preferably a tenter.

Examples Examples and comparative examples are shown below to explain the present invention in detail. However, the present invention is not limited to the embodiments. In addition, in the following embodiments, when not specifically stated, "%" means "mass %".

>Synthesis of isocyanate-reactive hydrocarbon compounds> (Synthesis Example 1: Inositol laurate) In the flask, 15.0 g (0.083 mol) of inositol, 75.1 g (0.375 mol) of lauric acid, 90.0 g of toluene, 2.0 g of p-toluenesulfonic acid, and 0.5 g of sulfuric acid were added. The solution was heated to reflux, and a Dean-Stark Trap was used to remove water from the reaction system. Once all the water was removed, the reaction was cooled to 70° C., and 13.0 g of 10% by mass sodium hydroxide solution was added. The reaction was stirred for 1 hour and cooled to room temperature. Vacuum filtration was performed, and the recovered solid was dried in an oven under reduced pressure overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 123.2 mgKOH/g.

(Synthesis Example 2: Inositol stearate) In the flask, 15.0 g (0.083 mol) of inositol, 106.5 g (0.374 mol) of stearic acid, 90.0 g of toluene, 2.0 g of p-toluenesulfonic acid and 0.5 g of sulfuric acid were added. The solution was heated to reflux, and a Dean-Stark Trap was used to remove water from the reaction system. Once all the water was removed, the reaction was cooled to 70° C., and 13.0 g of 10% by mass sodium hydroxide solution was added. The reaction was stirred for 1 hour and cooled to room temperature. Vacuum filtration was performed, and the recovered solid was dried overnight in a vacuum oven. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 89.6 mgKOH/g.

(Synthesis Example 3: Mannitol behenate) In a flask, 12 g (0.066 mol) of mannitol, 56 g (0.164 mol) of behenic acid and 5.0 g of a 10% by mass sodium hydroxide solution were added, and heated at about 220° C. for 4 hours. The reactant was cooled to 80° C., and 0.48 g of 85% by mass phosphoric acid solution was added. The reaction was stirred for 1 hour, cooled to room temperature and then vacuum filtered. The solid was recovered and allowed to dry overnight in a vacuum oven. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 268.8 mgKOH/g.

(Synthesis Example 4: Xylitol behenate) 12 g (0.079 mol) of xylitol, 40.2 g (0.118 mol) of behenic acid and 5.0 g of 10% by mass sodium hydroxide solution were added to the flask. The reactor was heated at approximately 220°C for 4 hours. The reactant was cooled to 80° C., and 0.48 g of 85% by mass phosphoric acid solution was added. The reaction was stirred for 1 hour, cooled to room temperature and then vacuum filtered. The solid was recovered and allowed to dry overnight in a vacuum oven. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 470.4 mgKOH/g.

(Synthesis Example 5: Xylose palmitate) In a flask, 5.0 g (0.033 mol) of xylose, 22.9 g (0.083 mol) of palmitic acid chloride and 50.0 g of methylene chloride were added. The reaction was stirred at room temperature. Titrate 8.4g of triethylamine over 10 minutes. 5.0g of activated carbon was added to the reactor. The reaction was stirred for 1 hour and filtered. Dichloromethane was distilled off under reduced pressure. The remaining liquid is recovered and cooled to room temperature to solidify. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 179.2 mgKOH/g.

(Synthesis Example 6: Glucose palmitate) Into the flask were added 5.0 g (0.028 mol) of glucose, 26.7 g (0.097 mol) of chloroform and 70 g of methylene chloride. The reaction was stirred at room temperature. Titrate 9.8 g of triethylamine over 10 minutes. 10g of activated carbon was added to the reactor. The reaction was stirred for 1 hour and filtered. Dichloromethane was distilled off under reduced pressure. The remaining liquid is recovered and cooled to room temperature to solidify. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 123.2 mgKOH/g.

(Synthesis Example 7: Tristearyl citrate) 20.0 g (0.104 mol) of citric acid, 100.0 g (0.37 mol) of stearyl alcohol, 150 g of toluene and 2 g of sulfuric acid were added to the flask. The solution was heated to reflux, and a Dean-Stark Trap was used to remove water from the reaction system. After cooling to 0°C, the product was precipitated, filtered, and recrystallized using ethanol. The solid was recovered by filtration and allowed to dry overnight in a vacuum oven. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 58.8 mgKOH/g.

(Synthesis Example 8: Trimethylolpropane stearate) Place 190.6g (1.420mol) of trimethylolpropane, 808.2g (2.84mol) of stearic acid and 1.2g of p-toluenesulfonic acid in a flask, and perform dehydration reaction at 140~210℃ for 3 hours under nitrogen flow . The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 84.0 mgKOH/g.

(Synthesis Example 9: Di-trimethylolpropane stearate) Put 225.7g (0.902mol) of di-trimethylolpropane, 769.4g (2.705mol) of stearic acid and 5.0g of p-toluenesulfonic acid in a flask under nitrogen flow at 120~180℃ for 5.5 hours Dehydration reaction. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 53.2 mgKOH/g.

(Synthesis Example 10: Di-trimethylolpropane octadecyl carbamate) Put 4.4g (0.018mol) of di-trimethylolpropane, 4.6g of methyl isobutyl ketone and 15.6g (0.053mol) of octadecyl isocyanate in a flask, and react under a nitrogen flow at 80°C 1 hour. Let it dry overnight in a vacuum oven. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 50.4 mgKOH/g.

>Preparation of aqueous dispersions of isocyanate-reactive hydrocarbon compounds> Use EMASOL S-30V (desorbed sorbitan tristearate, manufactured by Kao Corporation), RIKEMAL B-150 (desorbed sorbitan tribehenate, manufactured by Riken Vitamin Co., Ltd.) and Synthesis Examples 1-10 Each of the isocyanate-reactive hydrocarbon compounds obtained was prepared as shown in Table 1, and the aqueous dispersion of the isocyanate-reactive hydrocarbon compound was prepared by the following procedure. 20 g of isocyanate-reactive hydrocarbon compounds and 20 g of methyl isobutyl ketone were added to the flask and melted at 80°C. In 78.7 g of ion-exchanged water, 1.0 g of stearylamine 30EO adduct and 0.3 g of acetic acid (90% aqueous solution) were dissolved and titrated at 80°C. Maintain the temperature and emulsify it with a high-pressure homogenizer (400 bar). Then, methyl isobutyl ketone was distilled off under reduced pressure, and ion-exchanged water was added to prepare an aqueous dispersion having a solid concentration of 21%. The content of isocyanate-reactive functional groups in the aqueous dispersion was calculated separately. In addition, the average particle diameter was measured separately. The average particle diameter is a particle diameter (median diameter) at which the percentage integrated value (volume basis) measured by a laser diffraction/scattering particle size distribution measuring device LA-300 (made by Horiba Manufacturing Co., Ltd.) is 50% (median particle diameter) (The same applies to the following production examples).

[Table 1]

>Preparation of aqueous dispersion of isocyanate compound> (Production Example 13) Into the flask, DURANATE24A-100 (biuret of hexamethylene diisocyanate, manufactured by Asahi Kasei Chemicals Co., Ltd., NCO%=23.5) 100g (NCO group 0.560mol) and methyl isobutyl ketone (MIBK) 65.9g Then start stirring. 53.8 g (0.560 mol) of 3,5-dimethylpyrazole was injected therein and kept at 50° C., and allowed to react until the isocyanate content became 0, whereby a blocked isocyanate compound was prepared. 30.8 g of MIBK, 65.9 g of propylene glycol monomethyl ether, and 0.31 g of octadecyltrimethylammonium chloride as a cationic surfactant were mixed and made into a uniform solution. After slowly injecting 175.8 g of ion-exchanged water while stirring, it was emulsified with a high-pressure homogenizer (400 bar). Then, the organic solvent was distilled off under reduced pressure, and ion-exchanged water was added to prepare an aqueous dispersion of an isocyanate compound having a solid content concentration of 20%. The obtained aqueous dispersion contained 0.73 mmol/g of crosslinkable functional groups (blocked isocyanate groups). The average particle size of this aqueous dispersion was 0.44 μm.

(Production Example 14) In the flask, add CORONATE L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosoh Corporation, NCO%=13.4, solid content concentration 75% ethyl acetate solution) 20.0g (NCO Base 0.064 mol) and methyl isobutyl ketone 15.0 g and stirred. Next, 5.6 g (0.064 mol) of methyl ethyl ketoxime was slowly added with a titration funnel, and the reaction was performed at 50 to 55° C. until the NCO content became 0%. After cooling, 1.4 g of an ethylene oxide adduct of tristyrylated phenol was added and homogenized. After slowly injecting 80 g of ion-exchanged water, it was emulsified using a high-pressure homogenizer (400 bar). After emulsification, the organic solvent was distilled off under reduced pressure, and ion-exchanged water was added to prepare an aqueous dispersion of an isocyanate compound with a solid content concentration of 21.4%. The obtained aqueous dispersion contained 0.62 mmol/g of crosslinkable functional groups (blocked isocyanate groups). The average particle size of this aqueous dispersion was 0.46 μm.

>Preparation of water-based dispersion of acrylic polymer> (Production Example 15) Put C6FMA (C ₆ F ₁₃ C ₂ H ₄ OC(O)C(CH ₃ )=CH ₂ )165.5g, acrylic 4- Hydroxybutyl ester 2.8g, n-dodecyl mercaptan 2.8g, EMULGEN E430 (polyoxyethylene (EO: 26) oleyl ether, manufactured by Kao Corporation) 10% diluted aqueous solution 69.0g, ARQUAD18-63 (alkane (C16-18) trimethylammonium chloride, manufactured by Lion Corporation (LION) 10% diluted aqueous solution 13.8g, PRONON204 (ethylene oxide propylene oxide polymer (the ratio of ethylene oxide is 40 mass %), manufactured by Nippon Oil & Fats Co., Ltd.), 13.8g of 10% diluted aqueous solution, 82.8g of dipropylene glycol, and 328.3g of ion-exchanged water. After heating at 55°C for 30 minutes, they were mixed using a homomixer. While maintaining the obtained mixed liquid at 50°C, it was treated with a high-pressure homogenizer at (400 bar) to prepare an emulsion. The resulting emulsion was placed in an autoclave and cooled to below 30°C. Add 107.6g of dichloroethylene and VA-061 (2,2'-azobis[2-(2-imidazolin-2-yl)propane], manufactured by Wako Pure Chemical Industries, Ltd.) in 10% diluted aqueous solution After 13.8 g of nitrogen was substituted in the gas phase, the polymerization reaction was carried out at 65° C. for 15 hours with stirring, and ion-exchanged water was added to prepare an aqueous dispersion of acrylic polymer having a solid content concentration of 20.7%. The average particle size of this aqueous dispersion was 0.10 μm. The resulting acrylic polymer contains fluorine atoms and chlorine atoms derived from perfluoroalkyl groups and vinylidene chloride.

(Production Example 16) In an autoclave, put 47.5g of stearyl acrylate, 2.5g of glycidyl methacrylate, 145g of pure water, 15g of tripropylene glycol, 1.5g of sorbitan monooleate, and polyoxyethylidene (EO: 18) 2 g of secondary alkyl (C12-14) ether and 1.5 g of dioctadecyl dimethyl ammonium chloride, which were emulsified and dispersed by ultrasound at 60° C. for 15 minutes under stirring. After nitrogen substitution in the autoclave, 0.5 g of 2,2-azobis(2-carboxamidopropane) dihydrochloride was added, and the reaction was carried out at 60°C for 3 hours. Add ion-exchanged water to adjust the solid content concentration to 22% to prepare an aqueous dispersion of acrylic polymer. The average particle size of this aqueous dispersion was 0.14 μm. The resulting acrylic polymer does not contain halogen atoms.

(Production Example 17) In an autoclave, put 20g of stearyl acrylate, 17.5g of lauryl acrylate, 2.5g of glycidyl methacrylate, 145g of pure water, 15g of tripropylene glycol, 1.5g of sorbitan monooleate, and polyoxygenated Ethyl (EO: 18) secondary alkyl (C12-14) ether 2g, dioctadecyl dimethyl ammonium chloride 1.5g, which was emulsified and dispersed by ultrasound at 60°C for 15 minutes with stirring. After nitrogen was replaced in the autoclave, 10 g of vinyl chloride was injected by pressurization, and 0.5 g of 2,2-azobis(2-carboxamidopropane) dihydrochloride was added and reacted at 60° C. for 3 hours. Add ion-exchanged water to adjust the solid content concentration to 22% to prepare an aqueous dispersion of acrylic polymer. The average particle size of this aqueous dispersion was 0.17 μm. The resulting acrylic polymer contains chlorine atoms derived from vinyl chloride.

(Production Example 18) Put 94g octadecyl acrylate in a flask, KF-2012 (radical reactive organic polysiloxane macromonomer, manufactured by Shin-Etsu Chemical Co., Ltd.) 4g, 2-hydroxyethyl methacrylate 2g, octadecyl Trimethylammonium chloride 1g, polyoxyethylene (EO: 7) lauryl ether 6g, polyoxyethylene (EO: 21) lauryl ether 2g, dodecyl mercaptan 0.1g, dipropylene glycol 30g and 190 g of ion-exchanged water was emulsified and dispersed by high-speed stirring at 50°C. Then, while maintaining the temperature at 40°C, it was treated with a high-pressure homogenizer (400 bar) to obtain an emulsion. 0.3 g of azobis(isobutylamidine) dihydrochloride was added to the emulsified product, and reacted at 60° C. for 10 hours under nitrogen ambient gas. Ion exchange water was added to adjust the solid content concentration to 21.8% to prepare an aqueous dispersion of acrylic polymer. The average particle size of this aqueous dispersion was 0.18 μm. The resulting acrylic polymer is an acrylic-polysiloxane polymer and does not contain halogen atoms.

(Production Example 19) Put C6FMA (C ₆ F ₁₃ C ₂ H ₄ OC(O)C(CH ₃ )=CH ₂ ) into the autoclave 209.5g, n-butyl methacrylate 34.9g, BLEMMER PE- 350 (polyethylene glycol monomethacrylate (containing approximately 10% by mass of polyethylene glycol dimethacrylate), manufactured by Nippon Oil & Fats Corporation) 6.98g, PRONON204 (ethylene oxide propylene oxide polymer (epoxy The ratio of ethane is 40% by mass), manufactured by Nippon Oil and Fats Co., Ltd.) 3.1g, NIKKOL AM-3130N (coconut oil fatty acid acetamidopropyl betaine solution, manufactured by Japan Surfactant Corporation) 3.1g, EMULGEN E430 Polyoxyethylene (EO: 26) oleyl ether, manufactured by Kao Corporation) 10.8g, water 434.2g, dipropylene glycol 104.8g and n-dodecyl mercaptan 3.5g, after heating at 60°C for 60 minutes, Using a high-pressure homogenizer, 100 bar pretreatment and 400 bar main treatment were used to prepare an emulsion. 714.8g of the resulting emulsion was put in an autoclave, and 1.4g of VA-061 (2,2'-azobis[2-(2-imidazolin-2-yl)propane], manufactured by Wako Pure Chemical Industries, Ltd.) was added. Cool to below 30℃. After the gas phase was substituted with nitrogen and 78.2 g of vinyl chloride was introduced, polymerization was carried out at 55°C for 1 hour and at 60°C for 10 hours with stirring, and ion-exchanged water was added to prepare acrylic acid polymerization with a solid content concentration of 20.9% The water-based dispersion of matter. The average particle size of this aqueous dispersion was 0.11 μm. The resulting acrylic polymer contains fluorine atoms and chlorine atoms derived from perfluoroalkyl groups and vinyl chloride.

[Examples 1 to 18 and Comparative Examples 1 to 5] >Modulation of water repellent> The compositions described in Table 2 and Table 3 were prepared, and the water-based dispersion of the isocyanate-reactive hydrocarbon compound and the water-based dispersion of the isocyanate compound were diluted and mixed to 100% by mass with water to prepare a water repellent. Tables 2 and 3 show the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound. In addition, in Table 3, PARADIT ZS (wax-zirconium water repellent; solid content concentration 24%; manufactured by Mingcheng Chemical Industry Co., Ltd.) and PETROX P-200 (wax water repellent; solid content concentration 34%; Mingcheng chemical industry (Manufactured by the company) are commercially available wax-based water repellents.

>Evaluation of water repellency and flame retardancy> PET plain woven card wool fabric (mass per unit area 138 g/m ² , undyed, non-flame retarded) was prepared as a test cloth. Next, the aforementioned water repellent is used as a processing fluid, and the test cloth is passed through the processing fluid by a continuous method, and an unnecessary solution is squeezed out using a rolling machine with a predetermined pressure, dried at 110°C for 1.5 minutes, and 170°C After 1 minute hardening, a processed cloth was produced. The suction rate is 92%.

(Water repellency evaluation) The processed fabric produced was evaluated according to the 7.2 water repellency test (spray test) of JIS L 1092:2009. The evaluation is carried out in accordance with the following criteria. When the performance is slightly good, "+" is attached to the rating, and when the performance is slightly degraded, "-" is attached to the rating. In addition, the 3-level or higher is considered as a pass. The results are shown in Table 2 and Table 3. 5: No moisture or adhesion of water droplets on the surface 4: The surface is not wet, but there are small water droplets attached 3: The surface shows moisture on each small water drop 2: Half of the surface appears wet, and each small wet penetrates the cloth 1: The entire surface appears wet

(Flame retardance evaluation) According to the provisions of the FMVSS-302 method (horizontal method, ISO3795), the flame retardancy was evaluated for the processed cloth prepared as described above. The self-extinguishment (flame retardancy) and self-extinguishment before the marking are set as qualified. Here, the so-called self-extinguishment before the marking line means that the test piece does not catch fire or self-extinguishes before the A-marking line. The so-called self-extinguishing means self-extinguishing within a burning distance of 51 mm (and within 60 seconds), or a burning speed of 102 mm/ Situations below min. The results are shown in Table 2 and Table 3.

[Table 2]

[table 3]

It is clear from the results shown in Tables 2 and 3 that when the water repellent agents of Examples 1 to 18 are used, the fibers can be provided with excellent water repellency, and the hindrance of the fiber's flame retardancy can be more effectively suppressed. In contrast, the water-repellent agents of Comparative Examples 1 to 4 cannot balance the excellent water-repellent and flame retardant hindering inhibitory effects.

[Examples 19 to 26 and Comparative Examples 6 to 9] >Modulation of water repellent> The composition described in Table 4 was prepared by diluting the water-based dispersion of the isocyanate-reactive hydrocarbon compound, the water-based dispersion of the isocyanate compound, and the water-based dispersion of the acrylic polymer to 100% by mass in total with water to prepare a water repellent . Table 4 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound. In addition, Table 4 shows the content (parts by mass) of the acrylic polymer with respect to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound. Comparative Examples 7 and 8 used commercially available wax-based water repellent, PARADIT ZS (wax-zirconium-based water repellent; solid content concentration 24%; manufactured by Mingcheng Chemical Industry Co., Ltd.) and PETROX P-200 (wax-based water repellent; Solid content concentration 34%; manufactured by Mingcheng Chemical Industry Company).

>Evaluation of water repellency and flame retardancy> Preparation of PET plain woven card wool (mass per unit area 138 g/m ² , undyed, non-flame retardant). Secondly, the following flame retardant treatment was carried out on the PET plain woven carded wool fabric to prepare a test cloth.

(Flame retardant treatment) Using a mini color dyeing machine, the bath ratio is set to 1:15. Use contains PHOSCON FR-V2 (phosphorus flame retardant; solid content concentration 44%; manufactured by Mingcheng Chemical Industry Company; 20% owf), DISPER GS-400 (dispersant; solid content concentration 55%; manufactured by Mingcheng Chemical Industry Company; 0.5g/L), acetic acid (90% aqueous solution; 0.3g/L) aqueous solution, the PET plain woven card felt was exhausted at 130°C for 30 minutes.

Secondly, the soaping step is to use an aqueous solution containing LACCOL NB (soaping agent; solid content concentration 71%; manufactured by Mingcheng Chemical Industry Co., Ltd.; 2.0g/L) and soda ash (2.0g/L). Wash the PET plain woven card for 15 minutes. After washing with hot water and washing with water, it was dried at 110°C for 2 minutes to prepare a test cloth that had been subjected to flame retardant treatment.

Next, the water-repellent agent in Table 4 was used as a working fluid, and it was set to the same as in Examples 1 to 18 and Comparative Examples 1 to 5. Using a continuous method, the test cloth was passed through the working fluid and squeezed with a predetermined pressure rolling machine Undesired solutions were dried at 110°C for 1.5 minutes and hardened at 170°C for 1 minute to produce processed cloth. The suction rate is 92%.

(Water repellency evaluation) The water repellency evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. Table 4 shows the results.

(Flame retardance evaluation) The flame retardancy evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. Table 4 shows the results.

[Table 4]

It is clear from the results shown in Table 4 that the water-repellent agents of Examples 20 to 26 contain acrylic polymers, but they are the same as those of Example 19 without acrylic polymers, which can impart excellent water-repellent properties to the fibers and are more effective Suppresses the flame retardancy of fibers. In contrast, the water-repellent agents of Comparative Examples 6 to 8 cannot balance the excellent water-repellent and flame retardant hindering inhibitory effects.

[Examples 27 to 31 and Comparative Examples 10 to 12] >Modulation of water repellent> The composition described in Table 5 was prepared, and the water-based dispersion of the isocyanate-reactive hydrocarbon compound, the water-based dispersion of the isocyanate compound, and the water-based dispersion of the acrylic polymer were diluted, mixed to 100% by mass with water, and a water repellent was prepared . Table 5 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound. In addition, Table 5 shows the content (parts by mass) of the acrylic polymer with respect to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound. For Comparative Example 10, a commercially available wax-based water repellent, PARADIT ZS (wax-zirconium-based water repellent; solid concentration 24%; manufactured by Mingcheng Chemical Industry Co., Ltd.) was used. In Comparative Example 11, AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent; manufactured by Asahi Glass Co., Ltd.), which is a commercially available C6 fluorine-based water repellent, was used.

>Evaluation of water repellency and flame retardancy> Prepare PET shower curtain (mass per unit area 125g/m ² , undyed, use flame retardant yarn). Secondly, the following flame retardant treatment was carried out on the PET shower curtain to prepare test cloth.

(Flame retardant treatment) Using a mini color dyeing machine, the bath ratio is set to 1:20. Use contains PHOSCON MK-PZ (brominated flame retardant; solid content concentration 48%; manufactured by Mingcheng Chemical Industry Company; 20% owf), DISPER FR-21N (dispersant; solid content concentration 77%; manufactured by Mingcheng Chemical Industry Company; 2.0% owf), acetic acid (90% aqueous solution; 0.3g/L) aqueous solution, the PET shower curtain was exhausted at 130°C for 30 minutes.

Secondly, the soaping step is to use UNISOLT F-SP (soaping agent; solid content concentration 79%; manufactured by Mingcheng Chemical Industry Co., Ltd.; 2.0g/L), CELLOPOLE PC-300 (chelating agent; solid content concentration 40%; Mingcheng Manufactured by Chemical Industry Corporation; 2.0g/L) and soda ash (2.0g/L) aqueous solutions, and the PET shower curtain that has been exhausted is washed at 80°C for 15 minutes. After washing with hot water and washing with water, it was dried at 110°C for 2 minutes to prepare a test cloth.

Next, the water-repellent agent in Table 5 was used as a working fluid, which was the same as in Examples 1 to 18 and Comparative Examples 1 to 5, using a continuous method to pass the test cloth through the working fluid and squeezing it with a rolling machine of a predetermined pressure Undesired solutions were dried at 110°C for 1.5 minutes and hardened at 170°C for 1 minute to produce processed cloth. The suction rate is 42%.

(Water repellency evaluation) The water repellency evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. In addition to the water repellency evaluation, the state of water leakage on the back of the test cloth after the spray test was visually observed, and the case where no stain was generated was evaluated as ○, and the case where the stain was generated was evaluated as ×. Table 5 shows the results.

(Flame retardance evaluation) The flame retardancy was evaluated by the 45° microburner method (3 seconds heating test) and the 45° coil method prescribed by the Japan Flameproof Association for performance testing of flameproof products. In the micro-lamp method, the after-flame time of 3 seconds or less is regarded as a pass, and in the coil law, the number of flame contact times is 3 or more as a pass. Table 5 shows the results.

[table 5]

It is clear from the results shown in Table 5 that the water-repellent agents of Examples 27 to 31 can impart excellent water-repellent properties to fibers, and can more effectively suppress the retardation of fiber flame retardancy. In contrast, the water-repellent agents of Comparative Examples 10 to 11 cannot balance the excellent water-repellent and flame retardant hindering inhibitory effects.

[Example 32 and Comparative Examples 13 to 15] >Modulation of water repellent> The composition described in Table 6 was prepared by diluting the water-based dispersion of the isocyanate-reactive hydrocarbon compound, the water-based dispersion of the isocyanate compound, the water-based dispersion of the acrylic polymer, and the phosphorus-based flame retardant to 100% by mass in total with water To prepare water repellent. Table 6 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound. In addition, Table 6 shows the content (parts by mass) of the acrylic polymer with respect to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound. Phosphorus flame retardant K-19A (phosphorus flame retardant; solid content concentration 100%; manufactured by Mingcheng Chemical Industry Co., Ltd.) is used. In Comparative Example 13, AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent; manufactured by Asahi Glass Co., Ltd.) and phosphorus-based flame retardant were used together in the market.

>Evaluation of water repellency and flame retardancy> Preparation of nylon high-density taffeta (mass per unit area 60g/m ² , dyed, non-flame-retardant treatment (in the treatment with water-repellent agent, flame retardant by phosphorus Agent for flame retardant treatment)) as a test cloth. Next, use the water repellent in Table 6 as a working fluid, using a continuous method to pass the test cloth through the working fluid, squeeze out the unnecessary solution using a calender with a predetermined pressure, dry at 110°C for 1.5 minutes, and dry at 170 It was cured at 1 degree C for 1 minute, and the processed cloth was produced. The suction rate is 42%.

(Water repellency evaluation) The water repellency evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. Table 6 shows the results.

(Flame retardance evaluation) The water repellency evaluation was performed as in Examples 27 to 31 and Comparative Examples 10 to 12. Table 6 shows the results.

[Table 6]

As is clear from the results shown in Table 6, the water-repellent agent of Example 32 can impart excellent water-repellent properties to fibers, and can more effectively suppress the retardation of fiber flame retardancy. On the other hand, the water-repellent agents of Comparative Examples 13 and 14 cannot balance the excellent water-repellent and flame-retardant inhibitory effects.

[Examples 33 to 34] >Modulation of water repellent> The composition described in Table 7 was prepared, and the water-based dispersion of the isocyanate-reactive hydrocarbon compound, the water-based dispersion of the isocyanate compound, and the water-based dispersion of the acrylic polymer were diluted and mixed to 100% by mass with water to prepare a water repellent. . Table 7 shows the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound. In addition, Table 7 shows the content (parts by mass) of the acrylic polymer with respect to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound.

>Evaluation of water repellency and flame retardancy> Preparation of PET plain woven card wool (mass per unit area 138 g/m ² , undyed, non-flame retardant). Secondly, the following flame retardant treatment was carried out on the PET plain woven carded wool fabric to prepare a test cloth.

(Flame retardant treatment) Using a mini color dyeing machine, the bath ratio is set to 1:15. Use contains PHOSCON FR-V2 (phosphorus flame retardant; solid content concentration 44%; manufactured by Mingcheng Chemical Industry Company; 20% owf), DISPER GS-400 (dispersant; solid content concentration 55%; manufactured by Mingcheng Chemical Industry Company; 0.5g/L), acetic acid (90% aqueous solution; 0.3g/L) aqueous solution, the PET plain woven card felt was exhausted at 130°C for 30 minutes.

Secondly, the soaping step is to use an aqueous solution containing LACCOL NB (soaping agent; solid content concentration 71%; manufactured by Mingcheng Chemical Industry Co., Ltd.; 2.0g/L) and soda ash (2.0g/L). Wash the PET plain woven card for 15 minutes. After washing with hot water and washing with water, it was dried at 110°C for 2 minutes to prepare a test cloth that had been subjected to flame retardant treatment.

Next, the water-repellent agent in Table 7 was used as a working fluid, which was the same as in Examples 1 to 18 and Comparative Examples 1 to 5, and the test cloth was passed through the working fluid by a continuous method, and squeezed with a predetermined pressure of a rolling mill Undesired solutions were dried at 110°C for 1.5 minutes and hardened at 170°C for 1 minute to produce processed cloth. The suction rate is 92%.

(Water repellency evaluation) The water repellency evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. Table 7 shows the results.

(Flame retardance evaluation) The flame retardancy evaluation was performed as in Examples 1 to 18 and Comparative Examples 1 to 5. Table 7 shows the results.

[Table 7]

(no)

Claims (14)

A water repellent is an aqueous dispersion in which at least a hydrocarbon compound having a functional group reactive with an isocyanate group and an isocyanate compound are dispersed in water, and the cross-linkable functional group of the aforementioned isocyanate compound is relative to the functional group of the aforementioned hydrocarbon compound The molar ratio is 0.3 or more. The water repellent agent according to claim 1, wherein the aforementioned hydrocarbon compound having a functional group reactive with an isocyanate group is a compound represented by the following general formula (1): W[-AR] _a [-B] _b (1) [In the general formula (1), W is an (a+b) valent organic group; A is bonded to W and is -XY- or -Y-; B is bonded to W and is -XZ or -Z; a is 1 Integer above; b is an integer above 1; (a+b) is 3-8; X is a divalent polyalkylene ether group; Y is a divalent group and is an ether group, an ester group, an amide group, Urethane group, urea group or thiocarbamate group; R is a linear or branched monovalent hydrocarbon group with 6 to 30 carbon atoms optionally containing at least one unsaturated bond; Z is hydroxyl, amine group, Carboxyl or thiol; however, when B is -XZ, Z is hydroxy]. The water repellent according to claim 1 or 2, wherein the aforementioned isocyanate compound is a blocked isocyanate. The water repellent according to any one of claims 1 to 3, which further contains a surfactant. The water repellent according to any one of claims 1 to 4, further comprising an acrylic polymer. The water repellent according to claim 5, wherein the content of the acrylic polymer is 0.1 to 99 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound in the water repellent. The water repellent according to claim 5 or 6, wherein the aforementioned acrylic polymer is an acrylic polymer containing a halogen element. The water repellent according to any one of claims 5 to 7, wherein the aforementioned acrylic polymer is an acrylic polymer containing no fluorine atom. The water repellent according to claim 5 or 6, wherein the aforementioned acrylic polymer is an acrylic polymer free of halogen elements. The water repellent according to any one of claims 5 to 9, wherein the aforementioned acrylic polymer is an acrylic-polysiloxane polymer. A water-repellent fiber product which has been treated with the water-repellent agent according to any one of claims 1 to 10. A method for manufacturing a water-repellent fiber product, comprising the step of contacting the water-repellent agent according to any one of claims 1 to 10 with a fiber product. A kit with: The first agent, which contains at least a hydrocarbon compound having a functional group reactive with an isocyanate group; and The second agent, which contains at least an isocyanate compound; The set is used to prepare a water-repellent agent. The water-repellent agent disperses the first agent and the second agent in water to make an aqueous dispersion user; The molar ratio of the crosslinkable functional group of the isocyanate compound in the second agent to the functional group of the hydrocarbon compound in the first agent is 0.3 or more. A kit with: The first agent contains at least a hydrocarbon compound having a functional group that can react with an isocyanate group; The second agent, which contains at least an isocyanate compound; and The third agent, which contains at least an acrylic polymer; The set is used to prepare a water-repellent agent. The water-repellent agent disperses the first agent, the second agent, and the third agent in water to make an aqueous dispersion user; The molar ratio of the crosslinkable functional group of the isocyanate compound in the second agent to the functional group of the hydrocarbon compound in the first agent is 0.3 or more.