JPWO2019240162A1 - Water repellent agent, water repellent fiber product, and method for producing the same - Google Patents

Abstract

Provided is a water repellent agent that imparts excellent water repellency to fibers and that does not easily impair the flame retardancy of the fibers. At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion in which an isocyanate compound is dispersed in water, with respect to the functional group of the hydrocarbon compound, of the crosslinkable functional group of the isocyanate compound A water repellent having a molar ratio of 0.3 or more.

Description

The present invention relates to a water repellent agent, a water repellent fiber product and a method for producing the same.

Conventionally, curtains, rugs, etc. used in public buildings such as hotels, inns, schools, hospitals, etc. are obliged to be provided with flame retardancy as flameproof articles by the Fire Service Law. In addition, upholstered fabrics, partitions, shoji papers, etc. are being recognized as flameproof articles.

In addition, these products are not satisfied simply by being excellent in flame retardancy, and are required to have functionality such as water repellency, antifouling property and antibacterial property. For example, shower curtains used in hotel bathrooms. For example, high water repellency is required.

Further, for example, it is indispensable to impart flame retardancy to vehicle interior materials such as car seats, but a water repellent is treated for the purpose of imparting antifouling properties.

As described above, many articles are required to have both excellent flame retardancy and water repellency, but it is known that most conventional water repellents significantly reduce flame retardancy.

As a technique for suppressing a decrease in flame retardancy due to a water repellent, for example, in Patent Document 1, a flame retardant yarn is used to increase the flame retardance of a fiber, and a very small amount of C8 fluorine-based repellent is used as a water repellent. A method of treating a flame-retardant yarn with a liquid agent is disclosed. Since the C8 fluorine-based water repellent can impart strong water repellency, it can impart water repellency even with a small amount of treatment. However, in recent years, it has been pointed out that perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) contained as impurities in C8 fluorine-based water repellents are toxic to living organisms and have a load on the environment. , C6 fluorine-based water repellents containing no such compounds, and further fluorine-free water repellents containing no fluorine atom are being used.

However, the C6 fluorine-based water repellent and the fluorine-free water repellent are inferior in water repellent performance to the C8 fluorine-based water repellent. For this reason, in order to impart sufficient water repellency to textile products, it is necessary to increase the amount used, while the flame retardancy decreases with the increase in the amount used, and therefore excellent flame retardancy and water repellency are achieved. It is difficult to achieve both.

Further, Patent Document 2 describes that flame retardancy and water repellency can be achieved at the same time by using a flame retardant yarn to enhance the flame retardancy of the fiber and treating a small amount of a wax-based water repellent as a water repellent. ing. However, it is difficult to impart sufficient water repellency to fibers with a wax-based water repellent.

Japanese Patent No. 2944835 JP, 2013-155459, A

The main object of the present invention is to provide a water-repellent agent that imparts excellent water repellency to fibers and that does not easily impair the flame retardancy of the fibers. Another object of the present invention is to provide a water repellent fiber product using the water repellent and a method for producing the same.

The present inventors have diligently studied to solve the above problems. As a result, at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion in which an isocyanate compound is dispersed in water, relative to the number of moles of the functional group of the hydrocarbon compound, the isocyanate compound By setting the ratio (molar ratio) of the number of moles of the crosslinkable functional group to a predetermined value, excellent water repellency is imparted to the fiber, and reduction in flame retardancy of the fiber is effectively suppressed. I found that. The present invention has been completed by further studies based on these findings.

That is, the present invention provides the inventions of the following modes.
Item 1. At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion of an isocyanate compound dispersed in water,
A water repellent, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the hydrocarbon compound is 0.3 or more.
Item 2. Item 2. The water repellent according to Item 1, wherein the hydrocarbon compound having a functional group capable of reacting with the isocyanate group is a compound represented by the following general formula (1).
W [-A-R] _a [-B] _b (1)
[In the general formula (1), W is an (a+b)-valent organic group. A is attached to W and is -X-Y- or -Y-. B is attached 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 to 8. X is a divalent polyalkylene ether group. Y is a divalent group and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which may optionally contain at least one unsaturated bond. Z is a hydroxy group, an amino group, a carboxy group or a thiol group. However, when B is -X-Z, Z is a hydroxy group. ]
Item 3. Item 3. The water repellent according to Item 1 or 2, wherein the isocyanate compound is a blocked isocyanate.
Item 4. Item 4. The water repellent according to any one of Items 1 to 3, further comprising a surfactant.
Item 5. Item 5. The water repellent agent according to any one of Items 1 to 4, further comprising an acrylic polymer.
Item 6. Item 6. The water repellent according to Item 5, wherein the content of the acrylic polymer is 0.1 to 99 parts by mass with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound in the water repellent.
Item 7. Item 7. The water repellent according to Item 5 or 6, wherein the acrylic polymer is an acrylic polymer containing a halogen element.
Item 8. Item 8. The water repellent according to any one of Items 5 to 7, wherein the acrylic polymer is an acrylic polymer containing no fluorine atom.
Item 9. Item 7. The water repellent according to Item 5 or 6, wherein the acrylic polymer is an acrylic polymer containing no halogen element.
Item 10. Item 10. The water repellent according to any one of Items 5 to 9, wherein the acrylic polymer is an acrylic-silicone polymer.
Item 11. Item 10. A water-repellent fiber product, which is treated with the water-repellent agent according to any one of items 1 to 10.
Item 12. Item 11. A method for producing a water-repellent textile product, which comprises a step of bringing the water-repellent agent according to any one of Items 1 to 10 into contact with the textile product.
Item 13. At least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group,
At least a second agent containing an isocyanate compound,
Equipped with
A kit for preparing a water repellent used as an aqueous dispersion, wherein the first agent and the second agent are dispersed in water,
The kit, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrocarbon compound of the first agent is 0.3 or more.
Item 14. At least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group,
At least a second agent containing an isocyanate compound,
At least a third agent containing an acrylic polymer,
Equipped with
A kit for preparing a water-repellent agent used as an aqueous dispersion, wherein the first agent, the second agent, and the third agent are dispersed in water,
The kit, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrocarbon compound of the first agent is 0.3 or more.

According to the present invention, it is possible to provide a water-repellent agent that imparts excellent water repellency to fibers and that does not easily impair the flame retardancy of the fibers. Further, according to the present invention, it is also possible to provide a water repellent fiber product using the water repellent and a method for producing the same.

1. Water repellent The water repellent of the present invention comprises a hydrocarbon compound having a functional group capable of reacting with an isocyanate group (hereinafter, may be referred to as “isocyanate-reactive hydrocarbon compound”), and an isocyanate compound dispersed in water. The water-based dispersion is characterized in that the ratio (molar ratio) of the number of moles of the crosslinkable functional group of the isocyanate compound to the number of moles of the functional group of the hydrocarbon compound is 0.3 or more. The water repellent of the present invention, by having such a constitution, imparts excellent water repellency to the fiber, and further, the inhibition of the flame retardancy of the fiber is effectively suppressed. Hereinafter, the water repellent of the present invention will be described in detail. In the following description, a one-liquid type water repellent composed of an aqueous dispersion in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are dispersed in water will be mainly described. Is a two-pack type kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound, wherein the first agent and the second agent are dispersed in water at the time of use to prepare an aqueous system. It may be in the form of a kit for preparing the water repellent of the present invention as a dispersion. Furthermore, in the present invention, a three-pack type kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound, a second agent containing an isocyanate compound, and a third agent containing an acrylic polymer is prepared. The agent, the second agent, and the third agent may be dispersed in water to prepare a kit for preparing the water repellent of the present invention as an aqueous dispersion.

(Isocyanate-reactive hydrocarbon compound)
The hydrocarbon compound having a functional group capable of reacting with an isocyanate group is a hydrocarbon compound in which a functional group capable of reacting with an isocyanate group is bonded to a hydrocarbon skeleton. As the isocyanate-reactive hydrocarbon compound, only one kind may be used, or two or more kinds may be mixed and used. The functional group capable of reacting with the isocyanate group is preferably a hydroxy group, an amino group, a carboxy group, a thiol group, or the like.

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

In the general formula (1), W is an (a+b)-valent organic group. A is attached to W and is -X-Y- or -Y-. B is attached 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 to 8. X is a divalent polyalkylene ether group. Y is a divalent group and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which may optionally contain at least one unsaturated bond. Z is a hydroxy group, an amino group, a carboxy group or a thiol group. However, when B is -X-Z, Z is a hydroxy group.

In the isocyanate-reactive hydrocarbon compound represented by the general formula (1), the hydroxy group, amino group, carboxy group or thiol group of the group Z becomes a functional group capable of reacting with the isocyanate group. 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 is preferably a residue of a polyfunctional compound. The group A and the 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 to 8. That is, the valence of the group W is 3 to 8. As the polyfunctional compound, a polyhydric alcohol compound, a polyvalent amine compound, a polyvalent carboxylic acid compound, and a polyvalent thiol compound are preferable.

The polyhydric alcohol compound is not limited, but can be selected from, for example, trimethylolethane, trimethylolpropane, ditrimethylolpropane, 1,2,4-butanetriol, glycerin and sugar alcohol. Sugar alcohols include, but are not limited to, aldoses and ketoses, such as compounds derived from tetroses, pentoses, hexoses and heptoses. Specific examples include glucose, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol. , Threitol, glucopyranose, mannopyranose, talopyranose, allopyranose, altropyranose, idopyranose, glopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, penta Examples thereof include erythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or a mixture thereof.

Examples of the polyvalent amine compound include, but are not limited to, diethylenetriamine, triethylenetetramine, aminoethylethanolamine, diethanolamine, triethanolamine and the like.

Polyvalent carboxylic acid compounds include, but are not limited to, malic acid, citric acid, and the like.

Examples of the polyvalent thiol compound include, but are not limited to, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate). ), dipentaerythritol hexakis (3-mercaptopropionate), and the like.

In A and B of the general formula (1), the group X is a divalent polyalkylene ether group (that is, a polyoxyalkylene group). Specific examples of the group X include homopolymers such as ethylene oxide, propylene oxide and butylene 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, a urethane group, a urea group, or a thiourethane group.

The group R is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which is bonded to the group Y and may optionally contain at least one unsaturated bond. As the carbon number of the hydrocarbon group, the lower limit is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and the upper limit is preferably 28 or less, more preferably 26 or less, further preferably Is 24 or less, and as a preferable range, 6 to 28, 6 to 26, 6 to 24, 8 to 30, 8 to 28, 8 to 26, 8 to 24, 10 to 30, 10 to 28, 10 to 26. , 10 to 24, 12 to 30, 12 to 28, 12 to 26, 12 to 24, and particularly preferably 12 to 24. Specific examples of the hydrocarbon group include decyl group, undecyl group, dodecyl group (lauryl group), myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, heneicosyl group, behenyl group, oleyl group. Groups and the like.

As a method for introducing the group R into the general formula (1), higher fatty acid (the carbon number includes carbon of carbonyl group), higher aliphatic alcohol, higher aliphatic monoisocyanate, higher aliphatic amine The method of reacting an alkyl halide, a fatty acid chloride or the like with a hydroxy group, a carboxy group, a thiol group, an amino group or the like of the above polyfunctional compound can be adopted. 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 the higher fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, and erucic acid. Can be mentioned.

Examples of the higher aliphatic alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, eicosanol, heneicosanol, behenyl alcohol and oleyl alcohol.

Examples of the higher aliphatic monoisocyanate include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, behenyl isocyanate and the like.

Examples of the higher aliphatic amine include decylamine, laurylamine, myristylamine, stearylamine, behenylamine, oleylamine and the like.

Examples of the alkyl halide include dodecyl chloride, hexadecyl chloride, octadecyl chloride, dodecyl bromide, hexadecyl bromide, octadecyl bromide and the like.

Examples of the fatty acid chloride include caprylic acid chloride, capric acid chloride, lauric acid chloride, myristic acid chloride, palmitic acid chloride, stearic acid chloride, oleyl acid chloride and the like.

The isocyanate-reactive hydrocarbon compound is preferably selected from the group consisting of the polyfunctional compound, the higher fatty acid, the higher aliphatic alcohol, the higher aliphatic monoisocyanate, the higher aliphatic amine, the alkyl halide, and the fatty acid chloride. It is preferably a reaction product with at least one of the above. The reaction product has a hydrocarbon skeleton derived from the polyfunctional compound, and has a functional group capable of reacting with an isocyanate group (preferably a hydroxy group, an amino group, a carboxy group, a thiol group) There is.

In the isocyanate-reactive hydrocarbon compound, the number of functional groups capable of reacting with the isocyanate group in one molecule is preferably 1 or more for the lower limit, and preferably 7 or less, more preferably 5 or less for the upper limit. It is more preferably 3 or less, and the range is preferably 1 to 7, more preferably 1 to 5, and further preferably 1 to 3.

(Isocyanate compound)
As the isocyanate compound, a known isocyanate compound (polyfunctional isocyanate compound) having two or more crosslinkable functional groups in one molecule can be used alone or in combination of two or more. In the present invention, the crosslinkable functional group of the isocyanate compound is specifically an isocyanate group or a blocked isocyanate group. Therefore, 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.

Further, as the isocyanate compound, a blocked isocyanate in which 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more of the isocyanate group is blocked with a blocking agent can be suitably used. As the blocked isocyanate, various known blocked isocyanates can be used. The blocked isocyanate can be prepared by reacting various known isocyanate compounds with various known blocking agents.

The isocyanate compound (including blocked isocyanate) may have a self-emulsifying property, and examples of the self-emulsifying isocyanate compound include, for example, a nonionic hydrophilic group, a cationic hydrophilic group, and an anionic part of the isocyanate compound. An isocyanate compound introduced with a hydrophilic group can be used, and from the viewpoint of water repellency, an isocyanate compound introduced with a nonionic hydrophilic group having an oxyethylene group can be preferably used. Examples of the hydrophilic compound that is reacted with an isocyanate compound to impart self-emulsifying property include polyoxyalkylenes such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol polypropylene glycol monomethyl ether, and polypropylene glycol polyethylene glycol monobutyl ether. Monoalkyl ethers; ethylene glycol, or (poly)ethylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol; polyethylene glycol, polypropylene glycol, polytetramethylene glycol block copolymers, random copolymers, ethylene oxide And propylene oxide, random copolymers and block copolymers of ethylene oxide and butylene oxide; polyoxyalkylene monoamines, polyoxyalkylene diamines; and the like, and polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, etc. are preferred. Used. The above nonionic hydrophilic compounds may be used alone or in combination of two or more. The self-emulsifying property can be imparted to the isocyanate compound by introducing a predetermined amount of these compounds into the isocyanate group. The introduction amount of these compounds is preferably 1 mol% or more for the lower limit and 50 mol% or less for the upper limit, more preferably 40 mol% or less, further preferably 30 mol% or less for the isocyanate group, The range is preferably about 1 to 50 mol%, more preferably about 1 to 40 mol%, and further preferably about 1 to 30 mol%.

Examples of the isocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate. Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Examples thereof include trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate. Examples of the alicyclic polyisocyanate include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and the like. Examples of the aromatic polyisocyanate include 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), bis-(4-isocyanatocyclohexyl)methane (hydrogenated MDI), norbornane diisocyanate, and the like. , 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl- 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like can be mentioned, and examples of the araliphatic polyisocyanate include 1 , 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α′,α′-tetramethylxylylene diisocyanate, and the like, and reactions of these compounds, for example, adduct type polyisocyanate and uretdione formation reaction It is also preferable to use an isocyanate-modified product obtained by an isocyanurate-forming reaction, a carbodiimidizing reaction, a uretonimine-forming reaction, a biuret-forming reaction, or a mixture thereof.

The blocking agent introduced into the isocyanate compound is a compound having one or more active hydrogen atoms in the molecule, and it can be used alone or in combination of two or more kinds. Examples of the blocking agent include alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, Examples thereof include carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds, imine compounds, pyrazole compounds, bisulfites and the like. Among them, acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds are preferable, and ε-caprolactam, acetylacetone, diethyl malonate, methylethylketone oxime, cyclohexanone oxime, 3-methylpyrazole, 3,5-dimethylpyrazole, etc. Can be preferably used.

In the water repellent of the present invention, the ratio (molar ratio) of the number of moles of the crosslinkable functional group of the isocyanate compound to the number of moles of the functional group of the isocyanate-reactive hydrocarbon compound may be 0.3 or more, From the viewpoint of effectively suppressing the inhibition of the flame retardance of the fiber while suitably imparting excellent water repellency to the fiber, the lower limit of the molar ratio is preferably 0.4 or more, more preferably the lower limit. It is 0.5 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, further preferably 4 or less, and the preferable range is about 0.3 to 8, about 0.3 to 6, and 0. 3-4, 0.4-8, 0.4-6, 0.4-4, 0.5-8, 0.5-6, 0.5-4, Particularly, about 0.5 to 4 is preferable.

In the water repellent of the present invention, the mass ratio of the isocyanate-reactive hydrocarbon compound and the isocyanate compound (isocyanate-reactive hydrocarbon compound:isocyanate compound) is not particularly limited, but excellent water repellency for fibers is preferable. From the viewpoint of effectively suppressing the inhibition of the flame retardancy of the fiber while imparting, it is preferably 1:0.001 to 1000, more preferably 1:0.05 to 20, and further preferably 1:0.1. 10.

The water repellent of the present invention may be a processing liquid having a concentration for treating a textile product as it is, or a stock solution diluted with water before being used for treating a textile product (for example, the stock solution is increased to 5 to 1000 times). It is diluted and used as a working fluid).

When the water repellent of the present invention is used as the 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. , More preferably 1.0% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and the preferred range is 0.01% by mass or less. -60 mass%, 0.01-50 mass%, 0.01-40 mass%, 0.5-60 mass%, 0.5-50 mass%, 0.5-40 mass% , About 1.0 to 60% by mass, about 1.0 to 50% by mass, about 1.0 to 40% by mass, and particularly about 1.0 to 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, It is more preferably 1.0% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and a preferable range is 0.01 to About 60% by mass, about 0.01 to 50% by mass, about 0.01 to 40% by mass, about 0.5 to 60% by mass, about 0.5 to 50% by mass, about 0.5 to 40% by mass, The amount is about 1.0 to 60% by mass, about 1.0 to 50% by mass, and about 1.0 to 40% by mass, and particularly preferably about 1.0 to 40% by mass.

In the water repellent of the present invention, the isocyanate-reactive hydrocarbon compound and the isocyanate compound may 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 an isocyanate-reactive hydrocarbon compound and particles of an isocyanate compound are dispersed in water. It may be an aqueous dispersion of particles containing a hydrogen compound and an isocyanate compound in one particle. Particles of an isocyanate-reactive hydrocarbon compound and particles of an isocyanate compound are dispersed in water to form an aqueous dispersion, by mixing an aqueous dispersion of an isocyanate-reactive hydrocarbon compound with an aqueous dispersion of an isocyanate compound, It can be easily prepared. Also, an aqueous dispersion of particles containing an isocyanate-reactive hydrocarbon compound and an isocyanate compound in one particle should be prepared by mixing the isocyanate-reactive hydrocarbon compound and the isocyanate compound and then dispersing them in an aqueous system. You can

The water repellent of the present invention may contain other components in addition to the isocyanate-reactive hydrocarbon compound, the isocyanate compound, and water. Other components preferably include acrylic polymers, surfactants, flame retardants, silicone compounds, and other additives. As the other components, only one kind may be used, or two or more kinds may be mixed and used. However, it is preferable that the water repellent of the present invention does not contain a C8 fluorine-based water repellent (a compound having a perfluoroalkyl group having 8 or more carbon atoms).

Note that, for example, an acrylic polymer can be suitably prepared as an aqueous dispersion, and therefore can be blended even when the water repellent of the present invention is a stock solution, or the water repellent of the present invention can be diluted with water. When the processing liquid is used, it may be mixed with water when the processing liquid is prepared. Further, the surfactant is preferably used for dispersing the isocyanate-reactive hydrocarbon compound and the isocyanate compound in water when the water repellent of the present invention is made into an aqueous dispersion, and therefore, the surfactant of the present invention is preferably used. It is preferable to add the liquid medicine even when it is a stock solution. The timing of adding other components to the water repellent may be appropriately selected. Hereinafter, the other components will be described in detail.

(Acrylic polymer)
From the viewpoint of water repellency and flame retardancy, the water repellent of the present invention may optionally contain an acrylic polymer. As the acrylic polymer, only one kind may be used, or two or more kinds may be mixed and used.

As the acrylic polymer, those known as an aqueous dispersion can be used. For example, from the viewpoint of imparting even more excellent water repellency to fibers, acrylic polymers containing fluorine atoms are preferable. From the viewpoint of obtaining excellent flame retardancy of the fiber, an acrylic polymer containing chlorine atom is preferable. It is also preferable to use an acrylic polymer containing no halogen element from the viewpoint of environmental consideration.

The acrylic polymer is a polymer obtained by polymerizing at least a (meth)acrylate monomer. As described below, an acrylic polymer containing a halogen atom is obtained by copolymerizing a monomer containing a halogen atom with a (meth)acrylate monomer.

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. This hydrocarbon group may be linear or branched, may be saturated hydrocarbon or unsaturated hydrocarbon, and may have an alicyclic or aromatic ring. You may have. Among these, linear ones are preferable, and linear alkyl groups are more preferable.

From the viewpoint of enhancing water repellency, the carbon number of the ester portion is preferably 12 or more, and preferably 30 or less, and more preferably 12 to 30. The carbon number of the ester portion is more preferably 21 or less, and further preferably 12 to 21. When the carbon number is within this range, the water repellency and the feel become particularly excellent. Particularly preferred as the ester moiety is a linear alkyl group having 12 to 18 carbon atoms.

Examples of the (meth)acrylate monomer include lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate and behenyl (meth)acrylate. One or more types can be used.

Further, as the (meth)acrylate monomer having a cyclic structure in the ester portion, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, naphthyl (meth) Acrylate, 4-morpholinoethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, glycidyl ( (Meth) acrylate etc. are mentioned and these 1 type or multiple types can be used.

Further, the (meth)acrylate monomer preferably contains a functional group having crosslinkability. Examples of the functional group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, and a carboxyl group. Specific examples include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, and hydroxymethyl. (Meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, vinyl monochloroacetate, glycidyl (meth)acrylate, 2-[(3 , 5-dimethylpyrazolyl)carbonylamino]ethyl(meth)acrylate and the like. One or more of these can be used.

Examples of the (meth)acrylate monomer include radical-reactive organopolysiloxane macromonomers. When the radical-reactive organopolysiloxane macromonomer is copolymerized in the acrylic polymer, the acrylic polymer becomes an acrylic-silicone polymer.

The radical-reactive organopolysiloxane macromonomer may have one or two or more radical-reactive groups in one molecule, and it is particularly preferable that the number is one. Examples of the radical-reactive group include an azo group, a mercapto group, a vinyl group, a styryl group, and a (meth)acryloyl group, and at least one of them can be used. As the reactive group, a (meth)acryloyl group is preferable because of easy radical copolymerization, easy synthesis, and easy availability of a commercial product. As such a radical-reactive organopolysiloxane macromonomer, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. X-22-174ASX, X-22-174BX, X-22-2426, KF-2012 etc. can be used.

In addition, as the other monomer that can be copolymerized with the (meth)acrylate monomer, another polymerizable monomer that is not the (meth)acrylate monomer, or an organopolysiloxane having a radical reactive group is used. Include other macromonomers and the like. Examples of the other monomer include styrene, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ether, acrylonitrile, alkylol acrylamide, maleic acid diester, and (meth)acrylic acid methoxypolyalkylene glycol. .. Other monomers are not limited to these examples.

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

As the acrylic polymer, for example, Japanese Patent No. 5572385, Japanese Patent No. 5585078, Japanese Patent No. 5678660, Japanese Patent Publication No. 2017-534713, Japanese Patent Publication No. 2017-536439, Japanese Patent Publication No. 2017-538793, Japanese Patent No. Those described in Japanese Patent No. 4927760, Japanese Patent No. 5398723, Japanese Patent No. 5500238, Japanese Patent No. 5626337, Japanese Patent No. 6015003, Japanese Patent No. 6249048, Japanese Patent No. 6280298, Japanese Patent No. 4996875, etc. Can also be preferably used.

The acrylic polymer may be a halogen atom-containing acrylic polymer or a halogen atom-free acrylic polymer. As described above, for example, from the viewpoint of imparting even more excellent water repellency to the fiber, an acrylic polymer containing a fluorine atom is preferable. From the viewpoint of obtaining excellent flame retardancy of the fiber, an acrylic polymer containing chlorine atom is preferable. Further, from the viewpoint of the environment, it is also preferable to use an acrylic polymer containing no halogen element such as a fluorine atom or a chlorine atom.

The acrylic polymer can be preferably prepared as an aqueous dispersion by, for example, emulsion polymerization. Therefore, by mixing the isocyanate-reactive hydrocarbon compound and the isocyanate compound prepared as the aqueous dispersion with the acrylic polymer prepared as the aqueous dispersion, the water repellent can be easily obtained.

When the water repellent of the present invention contains an acrylic polymer, the content of the acrylic polymer is preferably not less than 0.1 part by mass, more preferably not less than 0.1 part by mass based on 100 parts by mass of the total amount of the hydrocarbon compound and the isocyanate compound. The amount is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and the upper limit is preferably 99 parts by mass or less, more preferably 55 parts by mass or less, and further preferably 35 parts by mass or less. Yes, as a preferable range, 0.1-99 parts by mass, 0.1-55 parts by mass, 0.1-35 parts by mass, 0.5-99 parts by mass, 0.5-55 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, and particularly preferably 1.0 to 35 parts by mass.

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

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, Polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, acetylene glycol oxyethylene adduct, polyethylene Examples include glycol polypropylene glycol block copolymers and the like.

Examples of the anionic surfactant include sulfate ester salts of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkylbenzene sulfonates, polyoxyethylene alkyl sulphates, polyoxyethylene alkyl phenyl ether sulphates, vinyl sulphates. Examples include succinate.

Examples of the cationic surfactant include amine salt, amidoamine salt, quaternary ammonium salt, and imidazolinium salt. Specific examples include, but are not limited to, alkylamine salts, polyoxyethylene alkylamine salts, alkylamidoamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, Examples thereof include quaternary ammonium salt type surfactants such as dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, alkylisoquinolinium salt and benzethonium chloride.

Examples of the amphoteric surfactant include alkylamine oxides, alanines, imidazolinium betaines, amidobetaines, betaine acetate, and the like, and specifically, long-chain amine oxides, laurylbetaine, stearylbetaine, laurylcarboxyl. Examples thereof include methyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethyl amino acetic acid betaine.

When the water repellent of the present invention contains a surfactant, the content of the surfactant is preferably 0.5 part by mass or more, more preferably the lower limit with respect to 100 parts by mass of the solid content of the water repellent. Is 1 part by mass or more, more preferably 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, further preferably 10 parts by mass or less, and preferably As a range, about 0.5-30 mass parts, about 0.5-20 mass parts, about 0.5-10 mass parts, about 1-30 mass parts, about 1-20 mass parts, about 1-10 mass parts. , About 1.5 to 30 parts by mass, about 1.5 to 20 parts by mass, about 1.5 to 10 parts by mass, and particularly preferably about 1.5 to 10 parts by mass.

(Flame retardants)
From the viewpoint of further improving the flame retardancy of the fiber, the water repellent of the present invention may further contain a flame retardant. The flame retardant is not particularly limited, and for example, known flame retardants such as brominated flame retardants, phosphorus flame retardants, nitrogen flame retardants, metal salt flame retardants, silicon flame retardants, inorganic flame retardants, etc. are used. can do. As will be described later, the fiber product to be treated by the water repellent of the present invention may be previously subjected to flame retardant treatment, and these flame retardant may be used for the flame retardant treatment.

When a 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 working liquid is preferably 1% by mass or more, and the upper limit is preferably 40. Mass% or less, more preferably 30 mass% or less, further preferably 25 mass% or less, and the range is preferably about 1 to 40 mass%, more preferably about 1 to 30 mass%, and further preferably 1 to It may be about 25% by mass.

(Silicone compound)
The water repellent of the present invention may contain one or more silicone compounds.

As the silicone compound, for example, amino-modified silicone can be used. As the amino-modified silicone, any of those having an amino group introduced at the side chain of the siloxane structure, those having an amino group introduced at the end of the siloxane structure, and mixtures thereof may be used, and the amino group may be a monoamine. , A diamine, or a partially blocked diamine may be used. In the amino-modified silicone, from the viewpoint of water repellency, the amine equivalent is preferably 300 g/mol or more, and more preferably 20000 g/mol or less, and it is more preferable to use one having a weight of about 300 to 20000 g/mol. In consideration of water repellency, washing durability, texture, price, etc., the amount is more preferably 1000 g/mol or more, and further preferably 7000 g/mol or less, and further preferably 1000 to 7000 g/mol. As such an amino-modified silicone, a commercially available product can be selected and used. For example, WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., KF-867, KF-869 and KF-8004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Further, carbinol-modified silicone can also be used. As the carbinol-modified silicone, any of those in which a hydroxyl group is introduced into the side chain of the siloxane structure, one in which a hydroxyl group is introduced into the terminal of the siloxane structure, or a mixture thereof may be used. As such a carbinol-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003 etc. are used. You can

Also, a diol-modified silicone can be used. As the diol-modified silicone, any of those having a diol group introduced into the side chain of the siloxane structure, those having a diol group introduced into the terminal of the siloxane structure, and mixtures thereof may be used. As such a diol-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. X-22-176DX, X-22-176F, X-22-176GX-A etc. can be used.

Further, phenol-modified silicone can also be used. As the phenol-modified silicone, any of those in which a phenolic hydroxyl group is introduced into the side chain of the siloxane structure, one in which a phenolic hydroxyl group is introduced into the terminal of the siloxane structure, or a mixture thereof may be used. As such a phenol-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. KF-2201 etc. can be used.

Further, carboxyl-modified silicone can also be used. As the carboxyl-modified silicone, any of those in which a carboxyl group is introduced into the side chain of the siloxane structure, those in which a carboxyl group is introduced into the terminal of the siloxane structure, or a mixture thereof may be used. As such a carboxyl-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. X-22-3701E, X-22-162C etc. can be used.

Further, mercapto-modified silicone can also be used. As the mercapto-modified silicone, any of those having a mercapto group introduced at the side chain of the siloxane structure, those having a mercapto group introduced at the end of the siloxane structure, and mixtures thereof may be used. As such a mercapto-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. KF-2001, KF-2004, X-22-167B, X-22-167C etc. can be used.

Epoxy-modified silicone can also be used. As the epoxy-modified silicone, any of those having an epoxy group introduced into the side chain of the siloxane structure, those having an epoxy group introduced into the terminal of the siloxane structure, and mixtures thereof may be used. As such an epoxy-modified silicone, a commercially available product can be selected and used. For example, Shin-Etsu Chemical Co., Ltd. X-22-343, KF-101, KF-1001, X-22-163, X-22-163A, X-22-163B, X-22-163C, KF-105, X. -22-169AS, X-22-169B, X-22-173BX, X-22-173DX and the like can be used.

Fluoroalkyl-modified silicone can also be used. As the fluoroalkyl-modified silicone, a commercially available product can be selected and used, and for example, Fluorosil J15, Fluorosil D2, Fluorosil H418, Fluorosil L118 and the like manufactured by SILTECH can be used.

Further, long chain alkyl-modified silicone can also be used. The long-chain alkyl-modified silicone can be selected from commercially available products and used, for example, KF-412, KF-413, KF-414, KF-415, KF-4003, KF-4701, manufactured by Shin-Etsu Chemical Co., Ltd. KF-4917, KF-7235B, X-22-7322, BELSIL CDM 3526 VP, BELSIL CM 7026 VP, BELSIL SDM 5055 VP manufactured by Asahi Kasei Wacker Silicone Co., Ltd. can be used.

Further, long chain alkyl/aralkyl modified silicone can also be used. As the long-chain alkyl/aralkyl-modified silicone, a commercially available product can be selected and used, and for example, X-22-1877 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Further, long chain alkyl polyether modified silicone can also be used. As the long-chain alkyl polyether modified silicone, a commercially available product can be selected and used, and for example, Silube T308-16, Silube T310-A16, Silube J208-812 manufactured by SILTECH can be used.

Further, higher fatty acid amide-modified silicone can also be used. As the higher fatty acid amide-modified silicone, a commercially available product can be selected and used, and for example, KF-3935 manufactured by Shin-Etsu Chemical Co., Ltd. or the like can be used.

In addition, dimethyl silicone or methylphenyl silicone can also be used. A commercially available product can be selected and used as dimethyl silicone or methylphenyl silicone. For example, if it is dimethyl silicone, Shin-Etsu Chemical Co., Ltd. KF-96, KF-965, KF-968, KF-995, etc., and if it is methylphenyl silicone, Shin-Etsu Chemical Co., Ltd. KF-50, KF-54. , KF-56 and the like can be used.

Also, silanol terminated silicones can be used. As the silanol-terminated silicone, a commercially available product can be selected and used, and for example, X-21-5841 and KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Further, from the viewpoint of imparting anti-slip properties, a silicone resin compound can also be used. As the silicone resin, known products can be used, for example, organopolysiloxane having MQ, MDQ, MT, MTQ, MDT or MDTQ as a constituent, solid at 25° C. and having a three-dimensional structure. It is preferably siloxane. Here, M, D, T and Q are each (R ') represents the ₃ SiO _0.5 units, (R') ₂ SiO units, R'SiO _1.5 units and SiO ₂ units. R'represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Silicone resins are commonly known as MQ resins, MT resins or MDT resins and may have moieties designated MDQ, MTQ or MDTQ.

The silicone resin can also be obtained as a solution prepared by dissolving it in a suitable solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and a mixture of these solvents. Etc.

As such a silicone resin, a commercially available product can be selected and used. As the solution, for example, Shin-Etsu Chemical Co., Ltd. KF-7312J, KF-7312K, KF-7312L, KF-7312T, KF-9021L, etc. can be used. As the silicone resin alone, for example, Shin-Etsu Chemical Co., Ltd.'s KR-220L, KR-216, Toray Dow Corning's DOWSIL MQ-1600 Solid Resin, DOWSIL MQ-1640 Flake Resin, Asahi Kasei Wacker Silicone's SILRES MK POWDER, SILRES MK FLAKE, SILRES 604 and the like can be used.

It is also possible to use a known silane coupling agent. Examples of the silane coupling agent include silane coupling agents containing an epoxy group, an amino group, a mercapto group, an isocyanate group and the like. As such a silane coupling agent, a commercially available product can be selected and used. For example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and epoxy group-containing silane coupling agents such as KBM-303, KBM-402, KBM-403, KBE-402, and KBE-403 can be used. As the silane coupling agent, KBM-602, KBM-608, KBM-903, KBE-903, KBM-573 and the like, and as the mercapto group-containing silane coupling agent, KBM-802, KBM-803 and the like, isocyanate group KBE-9007 or the like can be used as the contained silane coupling agent.

When the water repellent of the present invention contains a silicone compound, the content of the silicone compound is preferably 0.01 parts by mass or more with respect to the total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound. The upper limit is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, further preferably 45 parts by mass or less, and the range is preferably about 0.01 to 100 parts by mass, more preferably 0. The amount is about 01 to 70 parts by mass, and more preferably about 0.01 to 45 parts by mass.

(Other additives)
The water-repellent agent of the present invention may contain any additive in addition to the above-mentioned other components as long as the effects of the present invention are produced. Examples of the additives include fatty acid esters such as various sorbitan derivatives, alkyl citrate derivatives, and pentaerythritol derivatives described in WO 2014/190905, hydrophobic compounds described in US Publication No. 2010/0190397, and Hydrophobic compounds, wax compounds, water repellent aid components, cross-linking agents (compounds different from isocyanate compounds), anti-slip agents, anti-wrinkle agents, flame retardants, antistatic agents, heat-resistant agents described in Kai 2017-222827. Examples include known additives such as agents for fibers such as agents, antioxidants, ultraviolet absorbers, pigments, metal powder pigments, rheology control agents, curing accelerators, deodorants, and antibacterial agents. For example, examples of the water repellent auxiliary component include zirconium compounds, and zirconium acetate, zirconium chloride, and zirconium nitrate are particularly preferable. These additives may 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 may be an aqueous dispersion dispersed in water, as described above, particles of the isocyanate-reactive hydrocarbon compound and particles of the isocyanate compound. The water-based dispersion in which is dispersed in water can be easily produced by mixing the water-based dispersion of the isocyanate-reactive hydrocarbon compound and the water-based dispersion of the isocyanate compound. Further, a water repellent agent further containing an acrylic polymer can be easily produced by mixing an aqueous dispersion of an acrylic polymer. An aqueous dispersion of particles containing an isocyanate-reactive hydrocarbon compound and an isocyanate compound in one particle can be produced by producing the isocyanate-reactive hydrocarbon compound and the isocyanate compound in the same water.

In the present invention, various aqueous dispersions may be produced by a known method, for example, a method of mixing various components and a surfactant and then adding water to disperse, or a machine using a known disperser or the like. And a method of physically dispersing. As the disperser, a homomixer, a homogenizer, a colloid mill, a line mixer, a bead mill, or the like can be used. Further, a known organic solvent may be added in the case of aqueous dispersion.

As described above, in the present invention, a two-pack type kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound is prepared, and the first agent and the second agent are used at the time of use. May be dispersed in water to prepare a kit for preparing the water repellent of the present invention as an aqueous dispersion. Furthermore, in the present invention, a three-pack type kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound, a second agent containing an isocyanate compound, and a third agent containing an acrylic polymer is prepared. The agent, the second agent, and the third agent may be dispersed in water to prepare a kit for preparing the water repellent of the present invention as an aqueous dispersion.

Specifically, the two-pack type kit of the present invention comprises at least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and at least a second agent containing an isocyanate compound, A kit for preparing a water repellent used as an aqueous dispersion, comprising a first agent and a second agent dispersed in water, comprising an isocyanate compound of a second agent for a functional group of a hydrocarbon compound of a first agent. The molar ratio of the crosslinkable functional group is 0.3 or more.

The three-pack type kit of the present invention comprises at least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, at least a second agent containing an isocyanate compound, and at least an acrylic polymer. A kit for preparing a water repellent for use as an aqueous dispersion, which comprises a third agent including a first agent, a second agent, and a third agent, the method comprising: The molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrogen compound is 0.3 or more.

The two-component type kit and the three-component type kit of the present invention are each used for preparing the above-described water repellent agent of the present invention. Therefore, the types and contents of the isocyanate-reactive hydrocarbon compound, isocyanate compound, acrylic polymer, and other components are the same as those of the water repellent of the present invention described above. In the case of, for example, a two-component type kit, at least one of the acrylic polymer and other components can be blended in the first agent and the second agent. Further, for example, in the case of a three-liquid type kit, the other components can be blended with at least one of the first agent, the second agent, and the third agent.

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

The fiber product treated with the water repellent of the present invention is not particularly limited as long as it is an article composed of fibers, for example, natural fibers such as cotton, silk, hemp, and wool, polyester, nylon, acrylic, Examples include synthetic fibers such as spandex and fiber products using these. In addition, there are no restrictions on the form and shape of textile products, and it is not limited to raw material shapes such as staples, filaments, tows, and threads, and various processing such as woven fabrics, knitting, stuffed cotton, non-woven fabrics, paper, sheets, films, etc. It may be in the form.

Further, the textile product may be subjected to a flame retardant treatment in advance. For example, in the case of polyester, flame-retardant treatment can be performed by appropriately selecting from the flame retardants described above in consideration of compatibility with the spinnability. The treatment method with the flame retardant is not particularly limited, and it may be added by simply adding it to the polymer or by copolymerizing it with polyester at the molecular level.

By using the water repellent of the present invention, a water repellent treatment can be performed on a textile product (cloth or the like) by a known method. Examples of the method for treating a textile product with the water repellent of the present invention include a continuous method and a batch method. When the water repellent of the present invention is a stock solution, a concentration suitable for the treatment (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 water repellent is diluted with water to prepare a working fluid so that

As a continuous method, it is also preferable to optionally add various chemicals such as a cross-linking agent in addition to water when preparing the processing liquid. Next, the object to be treated (that is, the textile product) is continuously fed into the impregnating device filled with the processing liquid to impregnate the object to be treated with the processing liquid, and then the unnecessary processing liquid is removed. The impregnating device is not particularly limited, and a padder, a kiss roll-type applying device, a gravure coater-type applying device, a spray-type applying device, a foam-type applying device, a coating-type applying device, and the like can be preferably used, and a padder-type is particularly preferable. Then, the operation which removes the water which remains in a processed material is performed using a drier. The dryer is not particularly limited, and a spreading dryer such as a hot flue or a tenter is preferable. The continuous method is preferably adopted when the object to be treated is in the form of cloth such as woven fabric.

Further, the batch method includes a step of immersing the object to be processed in a processing liquid and a step of removing water remaining in the object to be processed. The batch method is preferably employed when the material to be treated is not in the form of cloth, for example, when it is loose, top, sliver, skein, tow, yarn, or when it is not suitable for the continuous method such as knitting. In the step of dipping, for example, a cotton dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine or the like can be used. In the operation of removing water, a cheese dryer, a beam dryer, a hot air dryer such as a tumble dryer, a high frequency dryer, or the like can be used. It is preferable to perform dry heat treatment on the object to which the water repellent of the present invention is attached.

As for the temperature of the dry heat treatment, the lower limit is preferably 120° C. or higher, more preferably 160° C. or higher, and the upper limit is preferably 180° C. or lower, and the range is preferably 120 to 180° C. Especially, 160 to 180° C. is preferable. Regarding the time of the dry heat treatment, the lower limit 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 as a preferable range. Includes 10 seconds to 3 minutes, 10 seconds to 2 minutes, 1 to 3 minutes, and 1 to 2 minutes. The method of dry heat treatment is not particularly limited, but a tenter is preferable when the object to be treated is cloth-like.

The present invention will be described in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples. In the following examples, "%" means "mass%" unless otherwise specified.

<Synthesis of Isocyanate-Reactive Hydrocarbon Compound>
(Synthesis Example 1: Myo-inositol laurate)
15.0 g (0.083 mol) of myo-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 to the flask. The solution was heated to reflux and water was removed from the reaction system using a Dean-Stark trap. Once all the water was removed, the reaction was cooled to 70° C. and 13.0 g of 10 wt% sodium hydroxide solution was added. The reaction was stirred for 1 hour and cooled to room temperature. Vacuum filtered and the collected solid was dried under reduced pressure in an oven overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 123.2 mgKOH/g.

(Synthesis Example 2: Myo-inositol stearate)
To the flask were added 15.0 g (0.083 mol) of myo-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. The solution was heated to reflux and water was removed from the reaction system using a Dean-Stark trap. Once all the water was removed, the reaction was cooled to 70° C. and 13.0 g of 10 wt% sodium hydroxide solution was added. The reaction was stirred for 1 hour and cooled to room temperature. Vacuum filtered and the collected solid dried in a vacuum oven overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 89.6 mgKOH/g.

(Synthesis Example 3: mannitol behenate)
12 g (0.066 mol) of mannitol, 56 g (0.164 mol) of behenic acid, and 5.0 g of 10 mass% sodium hydroxide solution were added to the flask, and it heated at about 220 degreeC for 4 hours. The reaction was cooled to 80° C. and 0.48 g of 85 wt% phosphoric acid solution was added. The reaction was stirred for 1 hour, cooled to room temperature and then vacuum filtered. The solid was collected and dried in a vacuum oven overnight. 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 mass% sodium hydroxide solution were added to the flask. The reactor was heated at about 220° C. for 4 hours. The reaction was cooled to 80° C. and 0.48 g of 85 wt% phosphoric acid solution was added. The reaction was stirred for 1 hour, cooled to room temperature and then vacuum filtered. The solid was collected and dried in a vacuum oven overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 470.4 mgKOH/g.

(Synthesis example 5: xylose palmitate)
5.0 g (0.033 mol) of xylose, 22.9 g (0.083 mol) of palmitic acid chloride, and 50.0 g of dichloromethane were added to the flask. The reaction was stirred at room temperature. Triethylamine 8.4 g was added dropwise over 10 minutes. 5.0 g 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 was collected 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)
5.0 g (0.028 mol) of glucose, 26.7 g (0.097 mol) of palmitic acid chloride, and 70 g of dichloromethane were added to the flask. The reaction was stirred at room temperature. 9.8 g of triethylamine was added dropwise over 10 minutes. 10 g 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 was collected 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 water was removed from the reaction system using a Dean-Stark trap. After cooling to 0° C. to precipitate the product, the product was filtered and recrystallized with ethanol. The solid was collected by filtration and dried in a vacuum oven overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 58.8 mgKOH/g.

(Synthesis Example 8: trimethylolpropane stearate)
190.6 g (1.420 mol) of trimethylolpropane, 808.2 g (2.84 mol) of stearic acid and 1.2 g of p-toluenesulfonic acid were put in a flask, and dehydration reaction was performed at 140 to 210° C. for 3 hours under a nitrogen stream. I went. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 84.0 mgKOH/g.

(Synthesis Example 9: ditrimethylolpropane stearate)
225.7 g (0.902 mol) of ditrimethylolpropane, 769.4 g (2.705 mol) of stearic acid and 5.0 g of p-toluenesulfonic acid were placed in a flask, and under a nitrogen stream at 120 to 180° C. for 5.5 hours. A dehydration reaction was performed. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 53.2 mgKOH/g.

(Synthesis Example 10: Ditrimethylolpropane stearyl carbamate)
4.4 g (0.018 mol) of ditrimethylolpropane, 4.6 g of methyl isobutyl ketone and 15.6 g (0.053 mol) of stearyl isocyanate were placed in a flask and reacted at 80° C. for 1 hour under a nitrogen stream. Dried in a vacuum oven overnight. The hydroxyl value of the obtained isocyanate-reactive hydrocarbon compound was 50.4 mgKOH/g.

<Preparation of Aqueous Dispersion of Isocyanate-Reactive Hydrocarbon Compound>
Emazol S-30V (Sorbitan tristearate, manufactured by Kao), Rikemar B-150 (Sorbitan tribehenate, manufactured by Riken Vitamin), and the isocyanate-reactive hydrocarbon compounds obtained in Synthesis Examples 1 to 10 were used. An aqueous dispersion of an isocyanate-reactive hydrocarbon compound was prepared by the following procedure using the composition shown in Table 1. 20 g of an isocyanate-reactive hydrocarbon compound and 20 g of methyl isobutyl ketone were added to a flask and melted at 80°C. 1.0 g of a stearylamine 30EO adduct and 0.3 g of acetic acid (90% aqueous solution) were dissolved in 78.7 g of ion-exchanged water at 80° C. and added dropwise. The temperature was kept and emulsified with a high pressure homogenizer (400 bar). Thereafter, methyl isobutyl ketone was distilled off under reduced pressure, and ion-exchanged water was added to obtain an aqueous dispersion having a solid content concentration of 21%. The content of the isocyanate-reactive functional group in each aqueous dispersion was calculated. In addition, the average particle size was measured. The average particle diameter is a particle diameter (median particle diameter) measured by a laser diffraction/scattering particle diameter distribution measuring apparatus LA-300 (manufactured by Horiba, Ltd.) with a percentage integrated value (volume basis) of 50%. Yes (the same applies to the following production examples).

<Preparation of Aqueous Dispersion of Isocyanate Compound>
(Production Example 13)
A flask was charged with 100 g (NCO group: 0.560 mol) and methyl isobutyl ketone (MIBK): 65.9 g of Duranate 24A-100 (biuret body of hexamethylene diisocyanate, manufactured by Asahi Kasei Chemicals Corporation, NCO%=23.5) and stirred. Started. A blocked isocyanate compound was obtained by charging 53.8 g (0.560 mol) of 3,5-dimethylpyrazole therein, maintaining it at 50° C., and reacting it until the isocyanate content became zero. MIBK 30.8 g, propylene glycol monomethyl ether 65.9 g, and stearyl trimethyl ammonium chloride 0.31 g as a cationic surfactant were mixed to obtain a uniform solution. After gradually charging 175.8 g of ion-exchanged water with stirring, the mixture was emulsified with a high pressure homogenizer (400 bar). Thereafter, the organic solvent was distilled off under reduced pressure, and ion-exchanged water was added to obtain an aqueous dispersion of an isocyanate compound having a solid content concentration of 20%. The resulting aqueous dispersion contains 0.73 mmol/g of a crosslinkable functional group (blocked isocyanate group). The average particle size of this aqueous dispersion was 0.44 μm.

(Production Example 14)
In a flask, 20.0 g (NCO group 0.064 mol) and methyl isobutyl ketone of Coronate L (trimethylolpropane adduct of tolylene diisocyanate, manufactured by Tosoh Corporation, NCO%=13.4, solid content concentration 75% ethyl acetate solution) 15.0 g was added and stirred. Subsequently, 5.6 g (0.064 mol) of methyl ethyl ketone oxime was slowly added with a dropping funnel and reacted at 50 to 55° C. until the NCO content became 0%. After cooling, 1.4 g of ethylene oxide 30 mol adduct of tristyrenated phenol was added to homogenize. After gradually charging 80 g of ion-exchanged water, the mixture was emulsified with a high pressure homogenizer (400 bar). After completion of the emulsification, the organic solvent was distilled off under reduced pressure, and ion-exchanged water was added to obtain an aqueous dispersion of an isocyanate compound having a solid content concentration of 21.4%. The obtained aqueous dispersion contains a crosslinkable functional group (blocked isocyanate group) at 0.62 mmol/g. The average particle size of this aqueous dispersion was 0.46 μm.

<Preparation of acrylic polymer aqueous dispersion>
(Production Example 15)
_{Beaker, C6FMA (C 6 F 13 C} 2 H 4 OC (O) C (CH 3) = CH 2) 165.5g, 4- hydroxybutyl acrylate 2.8 g, n-dodecyl mercaptan 2.8 g, Emulgen E430 ( 13. 9.0 g of a 10% diluted aqueous solution of polyoxyethylene (EO:26) oleyl ether, manufactured by Kao Corporation, and a 10% diluted aqueous solution of ARCARD 18-63 (alkyl (C16-18) trimethylammonium chloride, manufactured by Lion Corporation) 13. 8 g, Pronone 204 (ethylene oxide propylene oxide polymer (ratio of ethylene oxide is 40% by mass), manufactured by NOF CORPORATION) 13.8 g of 10% diluted aqueous solution, dipropylene glycol 82.8 g, deionized water 328.3 g Was added, and the mixture was heated at 55° C. for 30 minutes and then mixed using a homomixer. The obtained mixed liquid was treated with a high pressure homogenizer (400 bar) while maintaining the temperature at 50° C. to obtain an emulsion. The obtained emulsion was placed in an autoclave and cooled to 30°C or lower. 107.6 g of vinylidene chloride and 13.8 g of a 10% dilute aqueous solution of an acetate salt of VA-061 (2,2′-azobis[2-(2-imidazolin-2-yl)propane], manufactured by Wako Pure Chemical Industries, Ltd.) were added. After the gas phase was replaced with nitrogen, the polymerization reaction was carried out at 65° C. for 15 hours while stirring, and ion-exchanged water was added to obtain an aqueous dispersion of an acrylic polymer having a solid content concentration of 20.7%. The average particle size of this aqueous dispersion was 0.10 μm. The obtained acrylic polymer contains a fluorine atom and a chlorine atom derived from a perfluoroalkyl group and vinylidene chloride.

(Production Example 16)
Stearyl acrylate 47.5 g, glycidyl methacrylate 2.5 g, pure water 145 g, tripropylene glycol 15 g, sorbitan monooleate 1.5 g, polyoxyethylene (EO:18) secondary alkyl (C12-14) ether 2 g, in an autoclave. 1.5 g of dioctadecyldimethylammonium chloride was added, and the mixture was emulsified and ultrasonically dispersed at 60° C. for 15 minutes while stirring. After replacing the inside of the autoclave with nitrogen, 0.5 g of 2,2-azobis(2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60° C. for 3 hours. Ion-exchanged water was added to adjust the solid concentration to 22% to obtain an aqueous dispersion of acrylic polymer. The average particle size of this aqueous dispersion was 0.14 μm. The resulting acrylic polymer contains no halogen atoms.

(Production Example 17)
Stearyl acrylate 20g, lauryl acrylate 17.5g, glycidyl methacrylate 2.5g, pure water 145g, tripropylene glycol 15g, sorbitan monooleate 1.5g, polyoxyethylene (EO:18) secondary alkyl (C12-14). ) 2 g of ether and 1.5 g of dioctadecyldimethylammonium chloride were added, and the mixture was emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After replacing the inside of the autoclave with nitrogen, 10 g of vinyl chloride was charged under pressure, 0.5 g of 2,2-azobis(2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60° C. for 3 hours. Ion-exchanged water was added to adjust the solid concentration to 22% to obtain an aqueous dispersion of acrylic polymer. The average particle size of this aqueous dispersion was 0.17 μm. The obtained acrylic polymer contains chlorine atoms derived from vinyl chloride.

(Production Example 18)
Stearyl acrylate 94 g, KF-2012 (radical-reactive organopolysiloxane macromonomer, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 g, 2-hydroxyethyl methacrylate 2 g, stearyl trimethyl ammonium chloride 1 g, polyoxyethylene (EO:7) lauryl ether. 6 g, 2 g of polyoxyethylene (EO:21) lauryl ether, 0.1 g of dodecyl mercaptan, 30 g of dipropylene glycol and 190 g of ion-exchanged water are put and emulsified and dispersed at 50° C. by high speed stirring. Then, it was treated with a high pressure homogenizer (400 bar) while keeping it at 40° C. to obtain an emulsion. To this emulsion, 0.3 g of azobis(isobutylamidine) dihydrochloride was added, and the mixture was reacted at 60° C. for 10 hours under a nitrogen atmosphere. Ion-exchanged water was added to adjust the solid concentration to 21.8% to obtain an acrylic polymer aqueous dispersion. The average particle size of this aqueous dispersion was 0.18 μm. The resulting acrylic polymer is an acrylic-silicone polymer and contains no halogen atoms.

(Production Example 19)
_{Autoclave, C6FMA (C 6 F 13 C} 2 H 4 OC (O) C (CH 3) = CH 2) 209.5g, n- butyl methacrylate 34.9 g, Blemmer PE-350 (polyethylene glycol monomethacrylate (polyethylene glycol Approximately 10% by mass of dimethacrylate), manufactured by NOF CORPORATION) 6.98 g, Pronone 204 (ethylene oxide propylene oxide polymer (ratio of ethylene oxide is 40% by mass), manufactured by NOF CORPORATION) 3.1 g, NIKKOL AM-3130N (coconut oil fatty acid amide propyl betaine solution, manufactured by Nippon Surfactant Co., Ltd.) 3.1 g, Emulgen E430 (polyoxyethylene (EO:26) oleyl ether, manufactured by Kao Corporation) 10.8 g, water 434.2 g, dipropylene After adding 104.8 g of glycol and 3.5 g of n-dodecyl mercaptan, the mixture was heated at 60° C. for 60 minutes, pretreated with a high-pressure homogenizer at 100 bar, and finally treated with 400 bar to obtain an emulsion. 714.8 g of the obtained emulsion was placed in an autoclave, and 1.4 g of VA-061 (2,2′-azobis[2-(2-imidazolin-2-yl)propane], Wako Pure Chemical Industries, Ltd.) was added. , Cooled to 30°C or lower. After replacing the gas phase with nitrogen and introducing 78.2 g of vinyl chloride, a polymerization reaction was carried out with stirring at 55° C. for 1 hour and 60° C. for 10 hours. An aqueous dispersion of polymer was obtained. The average particle size of this aqueous dispersion was 0.11 μm. The obtained acrylic polymer contains a fluorine atom and a chlorine atom derived from a perfluoroalkyl group and vinyl chloride.

[Examples 1 to 18 and Comparative Examples 1 to 5]
<Preparation of water repellent>
An aqueous dispersion of an isocyanate-reactive hydrocarbon compound and an aqueous dispersion of an isocyanate compound were diluted and mixed so as to have a composition shown in Tables 2 and 3 so as to be 100% by mass together with water. To prepare a water repellent. The molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the isocyanate-reactive hydrocarbon compound is shown in Tables 2 and 3. In Table 3, Paragit ZS (wax-zirconium-based water repellent; solid content concentration 24%; manufactured by Meisei Chemical Co., Ltd.) and Petrox P-200 (wax-based water repellent; solid content concentration 34%; Meisei Chemical Industry). (Commercially available) are commercially available wax-based water repellents.

<Evaluation of water repellency and flame retardancy>
As a test cloth, a PET tropical cloth (weight per unit area: 138 g/m ² , undyed, flame-retardant untreated) was prepared. Then, using the above water repellent as a working liquid, a test cloth is passed through the working liquid by a continuous method, and unnecessary solution is squeezed by a constant pressure mangle, and dried at 110°C for 1.5 minutes, 170°C. It was cured for 1 minute to obtain a work cloth. The pickup was 92%.

(Water repellency evaluation)
The obtained processed cloth was evaluated according to the 7.2 water repellency test (spray test) of JIS L 1092:2009. The evaluation was performed according to the following criteria. When the performance was slightly good, the grade was marked with "+", and when the performance was slightly poor, the grade was marked with "-". In addition, grade 3 or higher was passed. The results are shown in Tables 2 and 3.
5: No wetting on the surface or adhesion of water droplets 4: No wetting on the surface, but showing adhesion of small water droplets 3: Wetting on small individual water droplets on the surface 2: Wetting on half of the surface , With small individual wetting penetrating the cloth 1: Wetting over the entire surface

(Evaluation of flame retardancy)
Based on the regulations of FMVSS-302 method (horizontal method, ISO3795), the flame resistance of the processed cloth obtained above was evaluated. Passed self-extinguishing (flame retardant) and self-extinguishing before the marked line Here, self-extinguishing before the marking means that the test piece does not ignite or self-extinguishing before the A marking, and self-extinguishing property means self-extinguishing within a burning distance of 51 mm (and within 60 seconds), or It refers to the case where the burning rate is 102 mm/min or less. The results are shown in Tables 2 and 3.

As is clear from the results shown in Tables 2 and 3, when the water repellents of Examples 1 to 18 were used, excellent water repellency was imparted to the fiber, and further, the flame retardancy of the fiber was inhibited. It can be seen that it is effectively suppressed. On the other hand, the water repellents of Comparative Examples 1 to 4 were not able to achieve both excellent water repellency and flame retardancy inhibition suppression effect.

[Examples 19 to 26 and Comparative Examples 6 to 9]
<Preparation of water repellent>
Dilute the water-based dispersion of an isocyanate-reactive hydrocarbon compound, the water-based dispersion of an isocyanate compound, and the water-based dispersion of an acrylic polymer so as to have the composition shown in Table 4 so as to be 100% by mass together with water. , And mixed 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. Table 4 shows the content (parts by mass) of the acrylic polymer based on 100 parts by mass of the total amount of the hydrocarbon compound and the isocyanate compound. Comparative Examples 7 and 8 are commercially available wax-based water repellents such as Paragit ZS (wax-zirconium-based water repellent; solid content concentration 24%; manufactured by Meisei Chemical Industry Co., Ltd.) and Petrox P-200 (wax-based water repellent). Agent; solid content concentration 34%; manufactured by Meisei Chemical Industry Co., Ltd.).

<Evaluation of water repellency and flame retardancy>
A PET tropical cloth (weight per unit area: 138 g/m ² , undyed, flame-retardant untreated) was prepared. Next, the PET tropical cloth was subjected to the following flame retardant treatment to obtain a test cloth.

(Flame retardant treatment)
Using a mini color dyeing machine, the bath ratio was 1:15. Phoscon FR-V2 (phosphorus flame retardant; solid content concentration 44%; Meisei Chemical Industry Co., Ltd., 20% owf), Disper GS-400 (dispersant; solid content concentration 55%; Meisei Chemical Industry Co., Ltd. Exhaust treatment was performed on the PET tropical cloth at 130° C. for 30 minutes using an aqueous solution containing 0.5 g/L) of acetic acid (90% aqueous solution; 0.3 g/L).

Next, as a soaping process, exhaustion was performed using an aqueous solution containing Laccol NB (soaping agent; solid content concentration: 71%; manufactured by Meisei Chemical Industry Co., Ltd.; 2.0 g/L) and soda ash (2.0 g/L). The treated PET tropical cloth was 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 obtain a flame-retardant test cloth.

Next, using the water repellent of Table 4 as a working fluid, the test cloth was passed through the working fluid by a continuous method in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and the mangle was fixed. Unnecessary solution was squeezed, dried at 110° C. for 1.5 minutes, and cured at 170° C. for 1 minute to obtain a work cloth. The pickup was 92%.

(Water repellency evaluation)
Water repellency was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Table 4.

(Evaluation of flame retardancy)
Flame retardancy was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Table 4.

As is clear from the results shown in Table 4, the water repellents of Examples 20 to 26 contained an acrylic polymer, but as in Example 19 containing no acrylic polymer, excellent water repellency for fibers. It is found that the inhibition of the flame retardancy of the fiber is effectively suppressed. On the other hand, the water repellents of Comparative Examples 6 to 8 were not able to achieve both excellent water repellency and flame retardancy inhibition suppressing effect.

[Examples 27 to 31 and Comparative Examples 10 to 12]
<Preparation of water repellent>
Dilute the aqueous dispersion of the isocyanate-reactive hydrocarbon compound, the aqueous dispersion of the isocyanate compound, and the aqueous dispersion of the acrylic polymer so as to have the composition shown in Table 5 so as to be 100% by mass together with water. , And mixed to prepare a water repellent. 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. Table 5 shows the content (parts by mass) of the acrylic polymer based on 100 parts by mass of the total amount of the hydrocarbon compound and the isocyanate compound. As Comparative Example 10, a commercially available wax water repellent, Paragit ZS (wax-zirconium water repellent; solid content concentration 24%; manufactured by Meisei Chemical Industry Co., Ltd.) was used. Further, as Comparative Example 11, a commercially available C6 fluorine-based water repellent AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent manufactured by Asahi Glass Co., Ltd.) was used.

<Evaluation of water repellency and flame retardancy>
A PET shower curtain (unit weight: 125 g/m ² , undyed, using flame-retardant yarn) was prepared. Next, the PET shower curtain was subjected to the following flame retardant treatment to obtain a test cloth.

(Flame retardant treatment)
Using a mini color dyeing machine, the bath ratio was 1:20. Foscon MK-PZ (bromine flame retardant; solid content concentration 48%; Meisei Chemical Industry Co., Ltd., 20% owf), Disper FR-21N (dispersant; solid content concentration 77%; Meisei Chemical Industry Co., Ltd. Exhaust treatment was performed on the PET shower curtain at 130° C. for 30 minutes using an aqueous solution containing 2.0% owf) and acetic acid (90% aqueous solution; 0.3 g/L).

Next, as a soaping step, Unisolt F-SP (soaping agent; solid content concentration 79%; manufactured by Meisei Chemical Industry Co., Ltd.; 2.0 g/L), Cellopol PC-300 (chelating agent; solid content concentration 40%; Meisei Chemical Co., Ltd.) The PET shower curtain that had been subjected to exhaustion treatment was washed at 80° C. for 15 minutes using an aqueous solution containing Kogyo Co., Ltd.; 2.0 g/L) and soda ash (2.0 g/L). After washing with hot water and washing with water, it was dried at 110° C. for 2 minutes to obtain a test cloth.

Next, using the water repellent of Table 5, as a working fluid, the test cloth was passed through the working fluid by a continuous method in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and the mangle at a constant pressure was used. Unnecessary solution was squeezed, dried at 110° C. for 1.5 minutes, and cured at 170° C. for 1 minute to obtain a work cloth. The pickup was 42%.

(Water repellency evaluation)
Water repellency was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. Furthermore, in addition to the water repellency evaluation, after the spray test, visually observing the state of whether or not water is bleeding out on the back surface of the test cloth, ◯ indicates no stain, and ◯ indicates stain. Was evaluated as x. The respective results are shown in Table 5.

(Evaluation of flame retardancy)
The flame retardancy was evaluated by the 45° microburner method (3 second heating test) and the 45° coil method of the flameproof product performance test defined by the Japan Flameproof Association. The micro burner method passed the afterflame time of 3 seconds or less, and the coil method passed the flame contact number of 3 times or more. The results are shown in Table 5.

As is clear from the results shown in Table 5, the water repellents of Examples 27 to 31 impart excellent water repellency to the fiber, and further, the inhibition of the flame retardancy of the fiber is effectively suppressed. I understand that On the other hand, the water repellents of Comparative Examples 10 to 11 were not able to achieve both excellent water repellency and flame retardancy inhibition suppression effect.

[Example 32 and Comparative Examples 13 to 15]
<Preparation of water repellent>
100% by mass of 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 so as to have the composition shown in Table 6 together with water. To prepare a 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 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound. As the phosphorus-based flame retardant, K-19A (phosphorus-based flame retardant; solid content concentration 100%; manufactured by Meisei Chemical Industry Co., Ltd.) was used. Further, in Comparative Example 13, a commercially available C6 fluorine-based water repellent AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent; manufactured by Asahi Glass Co., Ltd.) and a phosphorus-based flame retardant were used in combination.

<Evaluation of water repellency and flame retardancy>
As a test cloth, nylon high density taffeta (weight per unit area: 60 g/m ² , dyed, flame-retardant untreated (when treated with a water repellent, flame-retarded with a phosphorus-based flame retardant)) was prepared. Next, using the water repellent of Table 6, as a working liquid, the test cloth was passed through the working liquid by a continuous method, and unnecessary solution was squeezed with a mangle of a constant pressure, followed by drying at 110° C. for 1.5 minutes. It was cured at ℃ for 1 minute to obtain a work cloth. The pickup was 42%.

(Water repellency evaluation)
Water repellency was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Table 6.

(Evaluation of flame retardancy)
Water repellency was evaluated in the same manner as in Examples 27 to 31 and Comparative Examples 10 to 12. The results are shown in Table 6.

As is clear from the results shown in Table 6, the water repellent of Example 32 imparts excellent water repellency to the fiber, and further, inhibition of the flame retardancy of the fiber is effectively suppressed. I understand. On the other hand, the water repellents of Comparative Examples 13 and 14 could not achieve both excellent water repellency and flame retardancy inhibition suppressing effect.

[Examples 33 to 34]
<Preparation of water repellent>
Dilute 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 so as to have the composition shown in Table 7 so as to be 100% by mass together with water. , And mixed 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. Table 7 shows the content (parts by mass) of the acrylic polymer based on 100 parts by mass of the total amount of the hydrocarbon compound and the isocyanate compound.

<Evaluation of water repellency and flame retardancy>
A PET tropical cloth (weight per unit area: 138 g/m ² , undyed, flame-retardant untreated) was prepared. Next, the PET tropical cloth was subjected to the following flame retardant treatment to obtain a test cloth.

(Flame retardant treatment)
Using a mini color dyeing machine, the bath ratio was 1:15. Phoscon FR-V2 (phosphorus flame retardant; solid content concentration 44%; Meisei Chemical Industry Co., Ltd., 20% owf), Disper GS-400 (dispersant; solid content concentration 55%; Meisei Chemical Industry Co., Ltd. Exhaust treatment was performed on the PET tropical cloth at 130° C. for 30 minutes using an aqueous solution containing 0.5 g/L) of acetic acid (90% aqueous solution; 0.3 g/L).

Next, as a soaping process, exhaustion was performed using an aqueous solution containing Laccol NB (soaping agent; solid content concentration: 71%; manufactured by Meisei Chemical Industry Co., Ltd.; 2.0 g/L) and soda ash (2.0 g/L). The treated PET tropical cloth was 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 obtain a flame-retardant test cloth.

Next, using the water repellent of Table 7 as a working liquid, the test cloth was passed through the working liquid by the continuous method in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and the mangle at a constant pressure was used. Unnecessary solution was squeezed, dried at 110° C. for 1.5 minutes, and cured at 170° C. for 1 minute to obtain a work cloth. The pickup was 92%.

(Water repellency evaluation)
Water repellency was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Table 7.

(Evaluation of flame retardancy)
Flame retardancy was evaluated in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Table 7.

Claims (14)

At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion of an isocyanate compound dispersed in water,
A water repellent, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound to the functional group of the hydrocarbon compound is 0.3 or more. The water repellent according to claim 1, wherein the hydrocarbon compound having a functional group capable of reacting with the isocyanate group is a compound represented by the following general formula (1).
W [-A-R] _a [-B] _b (1)
[In the general formula (1), W is an (a+b)-valent organic group. A is attached to W and is -X-Y- or -Y-. B is attached 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 to 8. X is a divalent polyalkylene ether group. Y is a divalent group and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which may optionally contain at least one unsaturated bond. Z is a hydroxy group, an amino group, a carboxy group or a thiol group. However, when B is -X-Z, Z is a hydroxy group. ] The water repellent according to claim 1 or 2, wherein the isocyanate compound is a blocked isocyanate. The water repellent according to any one of claims 1 to 3, further comprising a surfactant. The water repellent agent according to claim 1, 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 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound in the water repellent. .. The water repellent according to claim 5, wherein the acrylic polymer is an acrylic polymer containing a halogen element. The water repellent according to any one of claims 5 to 7, wherein the acrylic polymer is a fluorine atom-free acrylic polymer. The water repellent according to claim 5 or 6, wherein the acrylic polymer is an acrylic polymer containing no halogen element. The water repellent according to any one of claims 5 to 9, wherein the acrylic polymer is an acrylic-silicone polymer. A water-repellent fiber product, which is treated with the water-repellent agent according to any one of claims 1 to 10. A method for producing a water-repellent fiber product, comprising the step of bringing the water-repellent agent according to any one of claims 1 to 10 into contact with the fiber product. At least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group,
At least a second agent containing an isocyanate compound,
Equipped with
A kit for preparing a water repellent used as an aqueous dispersion, wherein the first agent and the second agent are dispersed in water,
The kit, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrocarbon compound of the first agent is 0.3 or more. At least a first agent containing a hydrocarbon compound having a functional group capable of reacting with an isocyanate group,
At least a second agent containing an isocyanate compound,
At least a third agent containing an acrylic polymer,
Equipped with
A kit for preparing a water repellent used as an aqueous dispersion, wherein the first agent, the second agent, and the third agent are dispersed in water,
The kit, wherein the molar ratio of the crosslinkable functional group of the isocyanate compound of the second agent to the functional group of the hydrocarbon compound of the first agent is 0.3 or more.