WO2019240162A1 - Water repellent agent, water repellent fiber product, and method for manufacturing same - Google Patents

Abstract

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

Description

Water repellent, water repellent fiber product and method for producing the same

The present invention relates to a water repellent, 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 give flame retardancy as flameproof articles under the Fire Service Act. There are also movements to certify chairs, partitions, shoji paper, etc. as flameproof articles.

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

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

Thus, in many articles, it is required to achieve both excellent flame retardancy and water repellency, but most conventional water repellents are known to significantly reduce the flame retardancy.

As a technique for suppressing the decrease in flame retardancy due to a water repellent, for example, in Patent Document 1, flame retardant yarn is used to increase the flame retardancy of a fiber, and a very small amount of C8 fluorine-based repellent is used as a water repellent. A method for treating a flame retardant yarn with a liquid 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 harmful to living organisms and have an impact on the environment. The C6 fluorine-based water repellent that does not contain these compounds and the use of fluorine-free water repellent that does not contain fluorine atoms are being converted.

However, C6 fluorine-based water repellents and fluorine-free water repellents are inferior in water repellency compared to C8 fluorine-based water repellents. For this reason, in order to impart sufficient water repellency to textile products, it is necessary to increase the amount used, while flame retardance decreases with increasing amount used, so excellent flame resistance and water repellency It is difficult to achieve both.

Patent Document 2 describes that both flame retardancy and water repellency can be achieved by using a flame retardant yarn to increase the flame retardancy of a 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 the fiber with a wax-based water repellent.

Japanese Patent No. 2944835 JP 2013-155659 A

The main object of the present invention is to provide a water-repellent agent that imparts excellent water repellency to a fiber and that hardly inhibits the flame retardancy of the fiber. 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 intensively 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 the isocyanate compound is dispersed in water, the isocyanate compound relative to the number of moles of the functional group of the hydrocarbon compound. By setting the ratio of the number of moles of the crosslinkable functional group (molar ratio) to a predetermined value, excellent water repellency is imparted to the fiber, and a decrease in the flame retardancy of the fiber is effectively suppressed. I found out. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion in which the isocyanate compound is 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 General Formula (1), W is an (a + b) -valent organic group. A is bonded to W and is —X—Y— or —Y—. B is bonded to W and is —XZ or —Z. a is an integer of 1 or more. b is an integer of 1 or more. (A + b) is 3 to 8. X is a divalent polyalkylene ether group. Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a straight-chain 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 -XZ, 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 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 a total of 100 parts by mass 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 11. 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 fiber product, comprising a step of bringing the water-repellent agent according to any one of Items 1 to 10 into contact with the fiber product.
Item 13. A first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
A second agent containing at least an isocyanate compound;
With
A kit for preparing a water repellent used as an aqueous dispersion in which the first agent and the second agent are dispersed in water,
The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st agent is 0.3 or more.
Item 14. A first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
A second agent containing at least an isocyanate compound;
At least a third agent comprising an acrylic polymer;
With
A kit for preparing a water repellent used as an aqueous dispersion in which the first agent, the second agent, and the third agent are dispersed in water,
The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st 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 hardly inhibits the flame retardancy of the fibers. Moreover, according to this invention, the water-repellent fiber product using the said water-repellent agent and its manufacturing method can also be provided.

1. Water-repellent agent The water-repellent agent of the present invention comprises a hydrocarbon compound having a functional group capable of reacting with an isocyanate group (hereinafter sometimes referred to as “isocyanate-reactive hydrocarbon compound”) and an isocyanate compound dispersed in water. The ratio of the number of moles of crosslinkable functional groups of the isocyanate compound to the number of moles of the functional groups of the hydrocarbon compound is 0.3 or more. The water repellent of the present invention is provided with such a configuration, thereby imparting excellent water repellency to the fiber, and further inhibiting the inhibition of the flame retardancy of the fiber. Hereinafter, the water repellent of the present invention will be described in detail. In the following description, the description will focus on a one-component type water repellent composed of an aqueous dispersion in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are dispersed in water. Is a two-component kit comprising a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound, and in use, the first agent and the second agent are dispersed in water, It is good also as a form of the kit which prepares the water repellent of this invention as a dispersion. Furthermore, in this invention, it is set as the 3 liquid type kit provided with the 1st agent containing an isocyanate-reactive hydrocarbon compound, the 2nd agent containing an isocyanate compound, and the 3rd agent containing an acrylic polymer, The agent, the second agent, and the third agent may be dispersed in water to form a kit for preparing the water repellent of the present invention as an aqueous dispersion.

(Isocyanate-reactive hydrocarbon compounds)
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. Only one type of isocyanate-reactive hydrocarbon compound may be used, or two or more types may be mixed and used. Preferred examples of the functional group capable of reacting with an isocyanate group include a hydroxy group, an amino group, a carboxy group, and a thiol group.

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 bonded to W and is —X—Y— or —Y—. B is bonded to W and is —XZ or —Z. a is an integer of 1 or more. b is an integer of 1 or more. (A + b) is 3 to 8. X is a divalent polyalkylene ether group. Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a straight-chain 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 -XZ, 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 is 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. A group A and a group B are bonded to the group W. a is an integer of 1 or more, b is an integer of 1 or more, and (a + b) is 3 to 8. That is, the valence of the group W is 3-8. As a polyfunctional compound, Preferably, a polyhydric alcohol compound, a polyvalent amine compound, a polyvalent carboxylic acid compound, and a polyvalent thiol compound are mentioned.

The polyhydric alcohol compound is not limited, and 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, compounds derived from aldoses and ketoses such as 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, gropyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, inditol, inositol, penta Erythritol, dipentaerythritol, boremitol, gluconic acid, glyceric acid, xylon , Galactaric acid, ascorbic acid, gluconic acid lactone, lactones glyceric acid, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof.

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

Examples of the polyvalent carboxylic acid compound include, but are not limited to, malic acid and citric acid.

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

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 single polymers such as ethylene oxide, propylene oxide, and butylene oxide, block copolymers obtained by combining two or more of these, and random copolymers.

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. The lower limit of the number of carbon atoms of the hydrocarbon group 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, even more preferably. Is 24 or less, and preferred ranges are 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. 10-24, 12-30, 12-28, 12-26, 12-24, and 12-24 are particularly preferable. 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 Groups and the like.

As a method for introducing the group R into the general formula (1), higher fatty acids (note that the carbon number includes carbon of the carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, higher aliphatic amines. , Alkyl halides, fatty acid chlorides, and the like, and a method of reacting the hydroxy group, carboxy group, thiol group, amino group and the like of the polyfunctional compound can be employed. Thereby, the bond of group Y and group R can be formed, and group R can be introduce | transduced into General formula (1).

Examples of higher fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, lignoceric acid, palmitoleic acid, linoleic acid, arachidonic acid, oleic acid, and erucic acid. Can be mentioned.

Examples of 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, and behenyl isocyanate.

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

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, and oleic acid chloride.

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

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

(Isocyanate compound)
Moreover, as an isocyanate compound, the well-known isocyanate compound (polyfunctional isocyanate compound) which has a 2 or more crosslinkable functional group in 1 molecule can be used individually by 1 type or in combination of 2 or more types as appropriate. 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 of the isocyanate compound and the blocked isocyanate group 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.

Isocyanate compounds (including blocked isocyanates) may have self-emulsifying properties. Examples of isocyanate compounds having self-emulsifying properties include nonionic hydrophilic groups, cationic hydrophilic groups, and anionic properties in part of isocyanate compounds. From the viewpoint of water repellency, an isocyanate compound into which a nonionic hydrophilic group having an oxyethylene group is preferably used can be used. Examples of hydrophilic compounds that are reacted with isocyanate compounds to impart self-emulsifying properties 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, and polyethylene glycol; block copolymers, random copolymers, and ethylene oxides of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol And propylene oxide, ethylene oxide and butyleneo Random copolymers or block copolymers of the side; polyoxyalkylene monoamines, polyoxyalkylene diamines; and the like, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether and the like are preferably used. The said nonionic hydrophilic compound may be used individually by 1 type, or may be used in combination of 2 or more type. By introducing a predetermined amount of these compounds with respect to the isocyanate group, self-emulsifying properties can be imparted to the isocyanate compound. The introduction amount of these compounds is preferably 1 mol% or more for the lower limit with respect to the isocyanate group, and preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less for the upper limit. The range is preferably about 1 to 50 mol%, more preferably about 1 to 40 mol%, and still more 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- Trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer diisocyanate and the like. Examples of the alicyclic polyisocyanate include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, etc. Examples of the aromatic polyisocyanate include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples include diisocyanate, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and the like. Examples of the aliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the reaction of these compounds. For example, adduct type polyisocyanate and urea It is also preferable to use an isocyanate-modified product obtained by a todionization reaction, an isocyanuration reaction, a carbodiimidization reaction, a ureton iminization reaction, a biuretization reaction, or a mixture thereof.

The blocking agent introduced into the isocyanate compound is a compound having at least one active hydrogen in the molecule, and can be used alone or in combination of two or more. 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, and bisulfites. Of these, acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds are preferable, and ε-caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, 3,5-dimethylpyrazole, and the like. 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 retardancy of the fiber while suitably imparting excellent water repellency to the fiber, the molar ratio is preferably about 0.4 or more, more preferably The upper limit is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. Preferred ranges are about 0.3 to 8, about 0.3 to 6, About 3-4, about 0.4-8, about 0.4-6, about 0.4-4, about 0.5-8, about 0.5-6, about 0.5-4, In particular, about 0.5 to 4 is preferable.

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

The water repellent of the present invention may be a processing solution having a concentration for treating a fiber product as it is, or a stock solution (for example, 5 to 1000 times the stock solution) used by diluting with water before being used for treating a textile product. It may be used as a processing liquid after dilution).

When the water repellent of the present invention is used as a stock solution, the lower limit of the content (solid content) of the isocyanate-reactive hydrocarbon compound is preferably 0.01% by mass or more, more preferably 0.5% by mass or more. 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 a preferable range is 0.01% by mass or more. ˜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, and about 1.0 to 40% by mass, and particularly preferably 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 isocyanate compound content (solid content) is preferably 0.01% by mass or more, more preferably 0.5% by mass or more. More preferably, it is 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. About 60 mass%, about 0.01 to 50 mass%, about 0.01 to 40 mass%, about 0.5 to 60 mass%, about 0.5 to 50 mass%, about 0.5 to 40 mass%, Examples thereof include 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, or an isocyanate-reactive carbonization agent. An aqueous dispersion of particles in which a hydrogen compound and an isocyanate compound are contained in one particle may be used. The aqueous dispersion in which the isocyanate-reactive hydrocarbon compound particles and the isocyanate compound particles are dispersed in water is obtained by mixing the aqueous dispersion of the isocyanate-reactive hydrocarbon compound and the aqueous dispersion of the isocyanate compound. It can be easily prepared. Also, an aqueous dispersion of particles in which an isocyanate-reactive hydrocarbon compound and an isocyanate compound are contained in one particle is also prepared by mixing the isocyanate-reactive hydrocarbon compound and the isocyanate compound and then dispersing in water. Can do.

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. Only one type of other components may be used, or two or more types 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).

For example, an acrylic polymer can be suitably prepared as an aqueous dispersion, so that it can be blended even when the water repellent of the present invention is a stock solution, or the water repellent of the present invention is diluted with water. When preparing the processing liquid, it may be blended with water when the processing liquid is prepared. The surfactant is preferably used to disperse the isocyanate-reactive hydrocarbon compound and isocyanate compound in water when the water-repellent agent of the present invention is used as an aqueous dispersion. It is also preferable to mix the liquid medicine when it is a stock solution. What is necessary is just to select suitably about the timing which adds another component to a water repellent. Hereinafter, other components will be described in detail.

(Acrylic polymer)
The water repellent of the present invention may contain an acrylic polymer as necessary from the viewpoint of water repellency and flame retardancy. Only one type of acrylic polymer may be used, or two or more types may be mixed and used.

As the acrylic polymer, those known as an aqueous dispersion can be used. For example, an acrylic polymer containing a fluorine atom is preferable from the viewpoint of imparting further excellent water repellency to the fiber. Further, from the viewpoint of obtaining excellent flame retardancy of the fiber, an acrylic polymer containing a chlorine atom is preferable. From the viewpoint of environmental considerations, it is also preferable to use an acrylic polymer that does not contain a halogen element.

The acrylic polymer is a polymer obtained by polymerizing at least a (meth) acrylate monomer. As will be described later, 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 or unsaturated, and has an alicyclic or aromatic ring. You may do it. Among these, those that are linear are preferable, and those that are linear alkyl groups are more preferable.

From the viewpoint of improving water repellency, the ester moiety preferably has 12 or more carbon atoms, more preferably 30 or less, and more preferably 12 to 30 carbon atoms. The number of carbon atoms in the ester moiety is more preferably 21 or less, and further preferably 12 to 21. When the carbon number is within this range, the water repellency and texture are 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, behenyl (meth) acrylate, and the like. One or more types can be used.

In addition, as the (meth) acrylate monomer having a cyclic structure in the ester moiety, 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, These 1 type or multiple can be used.

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. Specifically, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, 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.

Further, examples of the (meth) acrylate monomer include a radical reactive organopolysiloxane macromonomer. In the acrylic polymer, when the radical-reactive organopolysiloxane macromonomer is copolymerized, the acrylic polymer becomes an acrylic-silicone polymer.

The radical-reactive organopolysiloxane macromonomer may have one or more radical-reactive groups in one molecule, and particularly preferably 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 these can be used. The reactive group is preferably a (meth) acryloyl group from the viewpoint of easiness of radical copolymerization, easiness of synthesis, and availability of commercially available products. As such radical reactive organopolysiloxane macromonomer, a commercially available product can be selected and used. For example, X-22-174ASX, X-22-174BX, X-22-2426, KF-2012, etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Other monomers that can be copolymerized with the (meth) acrylate monomer include other polymerizable monomers that are not (meth) acrylate monomers, organopolysiloxanes having radical reactive groups, and Are different macromonomers. Examples of other monomers include styrene, vinyl chloride, vinylidene chloride, ethylene, vinyl acetate, vinyl alkyl ether, acrylonitrile, alkylol acrylamide, maleic acid diester, methoxypolyalkylene glycol (meth) acrylate, and the like. . 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 is 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, preferably 6 or less, and preferably 1 to 6.

Examples of the acrylic polymer include, 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. No. 4927760, Japanese Patent No. 5398723, Japanese Patent No. 5500368, Japanese Patent No. 5626337, Japanese Patent No. 6015003, Japanese Patent No. 6249048, Japanese Patent No. 6280298, Japanese Patent No. 4996875, etc. Can also be suitably used.

The acrylic polymer may be an acrylic polymer containing a halogen atom or an acrylic polymer not containing a halogen atom. As described above, for example, from the viewpoint of imparting further excellent water repellency to the fiber, an acrylic polymer containing a fluorine atom is preferable. Further, from the viewpoint of obtaining excellent flame retardancy of the fiber, an acrylic polymer containing a chlorine atom is preferable. From the viewpoint of environmental considerations, it is also preferable to use an acrylic polymer that does not contain a halogen element such as a fluorine atom or a chlorine atom.

The acrylic polymer can be suitably prepared as an aqueous dispersion by, for example, emulsion polymerization. For this reason, a water repellent is simply obtained by mixing the isocyanate-reactive hydrocarbon compound and isocyanate compound prepared as an aqueous dispersion and the acrylic polymer prepared as an aqueous dispersion.

When the water-repellent agent of the present invention contains an acrylic polymer, the content of the acrylic polymer is preferably 0.1 parts by mass or more with respect to the lower limit with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound. The upper limit 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. The preferred range is 0.1 to 99 parts by weight, 0.1 to 55 parts by weight, 0.1 to 35 parts by weight, 0.5 to 99 parts by weight, 0.5 to 55 parts by weight, 0.5 They are ˜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.

Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl 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 alkylol amide, alkyl alkanol amide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene And glycol polypropylene glycol block copolymer.

Examples of the anionic surfactant include sulfate esters of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Examples include succinate.

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

Examples of amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples include long-chain amine oxides, lauryl betaines, stearyl betaines, lauryl carboxy. Examples include methylhydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

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

(Flame retardants)
The water repellent of the present invention may further contain a flame retardant from the viewpoint of further improving the flame retardancy of the fiber. The flame retardant is not particularly limited. For example, a known flame retardant such as a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a metal salt flame retardant, a silicon flame retardant, or an inorganic flame retardant is used. can do. In addition, as described later, the fiber product to be treated by the water repellent of the present invention may be subjected to a flame retardant treatment in advance, and these flame retardants can be used for the flame retardant treatment.

When a flame retardant is used in combination with the water repellent of the present invention, the content (solid content) of the flame retardant in the working fluid is preferably 1% by mass or more for the lower limit, and preferably 40 for the upper limit. % By mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less. The range is preferably about 1 to 40% by mass, more preferably about 1 to 30% by mass, and further preferably 1 to About 25 mass% is mentioned.

(Silicone compound)
One or more silicone compounds can be used in the water repellent of the present invention.

For example, amino-modified silicone can be used as the silicone compound. As the amino-modified silicone, any of those having an amino group introduced into the side chain of the siloxane structure, those having an amino group introduced into the terminal of the siloxane structure, or a mixture thereof may be used. A diamine or a partly 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 preferably 20000 g / mol or less, more preferably about 300 to 20000 g / mol. In consideration of water repellency, washing durability, texture, price, and the like, it is more preferably 1000 g / mol or more, more preferably 7000 g / mol or less, and further preferably 1000 to 7000 g / mol. Such amino-modified silicone can be selected from commercial products. For example, WACKER FINISH WR301, WR1100, WR1200, WR1300, WR1600 manufactured by Asahi Kasei Wacker Silicone, KF-867, KF-869 and KF-8004 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Carbinol-modified silicone can also be used. As the carbinol-modified silicone, any of those having a hydroxyl group introduced into the side chain of the siloxane structure, those having a hydroxyl group introduced into the terminal of the siloxane structure, or a mixture thereof may be used. Such carbinol-modified silicone can be selected from commercial products. For example, X-22-4039, X-22-4015, X-22-170BX, X-22-170DX, KF-6000, KF-6001, KF-6002, KF-6003 etc. manufactured by Shin-Etsu Chemical Co., Ltd. are used. Can do.

Diol-modified silicone can also 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, or a mixture thereof may be used. Such a diol-modified silicone can be selected from commercial products. For example, X-22-176DX, X-22-176F, X-22-176GX-A manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Also, phenol-modified silicone can be used. As the phenol-modified silicone, any of those having a phenolic hydroxyl group introduced into the side chain of the siloxane structure, those having a phenolic hydroxyl group introduced to the terminal of the siloxane structure, or a mixture thereof may be used. Such a phenol-modified silicone can be selected from commercial products. For example, KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Also, carboxyl-modified silicone can be used. As the carboxyl-modified silicone, any of those having a carboxyl group introduced into the side chain of the siloxane structure, those having a carboxyl group introduced into the terminal of the siloxane structure, or a mixture thereof may be used. Such carboxyl-modified silicone can be selected from commercial products. For example, X-22-3701E and X-22-162C manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Mercapto-modified silicone can also be used. As the mercapto-modified silicone, any of those having a mercapto group introduced into the side chain of the siloxane structure, those having a mercapto group introduced into the terminal of the siloxane structure, or a mixture thereof may be used. Such mercapto-modified silicone can be selected from commercial products. For example, KF-2001, KF-2004, X-22-167B, X-22-167C, etc. manufactured by Shin-Etsu Chemical Co., Ltd. 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 to the terminal of the siloxane structure, or a mixture thereof may be used. Such epoxy-modified silicone can be selected from commercial products. For example, X-22-343, KF-101, KF-1001, X-22-163, X-22-163A, X-22-163B, X-22-163C, KF-105, X manufactured by Shin-Etsu Chemical Co., Ltd. -22-169AS, X-22-169B, X-22-173BX, X-22-173DX, and the like can be used.

Fluoroalkyl-modified silicone can also be used. The fluoroalkyl-modified silicone can be selected from commercially available products, and examples thereof include Fluorosil J15, Fluorosil D2, Fluorosil H418, and Fluorosil L118 manufactured by SILTECH.

Also, long chain alkyl-modified silicones can be used. The long-chain alkyl-modified silicone can be selected from commercially available products, such as 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.

Also, long-chain alkyl / aralkyl-modified silicones can be used. The long-chain alkyl / aralkyl-modified silicone can be selected from commercially available products, for example, X-22-1877 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Also, long chain alkyl / polyether-modified silicones can be used. The long-chain alkyl / polyether-modified silicone can be selected from commercially available products, and examples thereof include Silube T308-16, Silube T310-A16, Silube J208-812, etc. manufactured by SILTECH.

Also, higher fatty acid amide-modified silicones can be used. The higher fatty acid amide-modified silicone can be selected from commercially available products. For example, KF-3935 manufactured by Shin-Etsu Chemical Co., Ltd. can be used.

Also, dimethyl silicone and methylphenyl silicone can be used. Commercially available products can be selected and used as dimethyl silicone and methylphenyl silicone. For example, KF-96, KF-965, KF-968, KF-995 manufactured by Shin-Etsu Chemical Co., Ltd. are used for dimethyl silicone, and KF-50, KF-54 manufactured by Shin-Etsu Chemical Co., Ltd. are used for methylphenyl silicone. KF-56 or the like can be used.

Silanol-terminated silicone can also be used. The silanol-terminated silicone can be selected from commercially available products, such as X-21-5841 and KF-9701 manufactured by Shin-Etsu Chemical Co., Ltd.

Moreover, a silicone resin compound can also be used from a viewpoint of provision of slip prevention property. As the silicone resin, known materials can be used. For example, organopolysiloxane having MQ, MDQ, MT, MTQ, MDT or MDTQ as a component, solid at 25 ° C., and having a three-dimensional structure. Siloxane is preferred. Here, M, D, T, and Q represent (R ′) ₃ SiO _0.5 unit, (R ′) ₂ SiO unit, R′SiO _1.5 unit, and SiO ₂ unit, respectively. R ′ represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Silicone resins are commonly known as MQ resins, MT resins, or MDT resins, and may have portions designated as MDQ, MTQ, or MDTQ.

The silicone resin can also be obtained as a solution in which it is dissolved in an appropriate solvent. Examples of the solvent include relatively low molecular weight methylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, n-hexane, isopropyl alcohol, methylene chloride, 1,1,1-trichloroethane, and mixtures of these solvents. Etc.

Such a silicone resin can be selected from commercial products. As the solution, for example, KF-7312J, KF-7312K, KF-7312L, KF-7312T, KF-9021L manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Examples of the silicone resin alone include KR-220L and KR-216 manufactured by Shin-Etsu Chemical Co., Ltd., DOWSIL MQ-1600 Solid Resin manufactured by Toray Dow Corning Co., Ltd., DOWSIL MQ-1640 Flask Resin, and SILRES MK POWDER manufactured by Asahi Kasei Silicone. SILRES MK FLAKE, SILRES 604, etc. can be used.

Also, it is 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. A commercial item can be selected and used for such a silane coupling agent. For example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Examples of the epoxy group-containing silane coupling agent include KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, etc. Examples of silane coupling agents include KBM-602, KBM-608, KBM-903, KBE-903, and KBM-573. Examples of mercapto group-containing silane coupling agents include KBM-802, KBM-803, and isocyanate groups. As the containing silane coupling agent, KBE-9007 or the like can be used.

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 lower limit with respect to 100 parts by mass in total 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, still more 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, more preferably about 0.01 to 45 parts by mass.

(Other additives)
The water repellent of the present invention may contain any additive as long as the effects of the present invention are produced, in addition to the other components described above. Examples of additives include various sorbitan derivatives described in International Publication No. 2014/190905, fatty acid esters such as alkyl citrate derivatives and pentaerythritol derivatives, hydrophobic compounds described in US Publication No. 2010/0190397, Hydrophobic compounds, wax-based compounds, water-repellent auxiliary components, crosslinking agents (compounds different from isocyanate compounds), anti-slip agents, anti-wrinkle agents, flame retardants, anti-static agents, heat resistance Examples include known additives such as textile agents 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 hydrochloride, and zirconium nitrate are particularly preferable. These additives can be used singly or in appropriate 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, the isocyanate-reactive hydrocarbon compound particles, the isocyanate compound particles, An aqueous dispersion in which is dispersed in water can be easily produced by mixing an aqueous dispersion of an isocyanate-reactive hydrocarbon compound and an aqueous dispersion of an isocyanate compound. Moreover, the water repellent which further contains an acrylic polymer by mixing the aqueous dispersion of an acrylic polymer can also be manufactured easily. 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, after mixing various components and a surfactant, water is added and dispersed, or a known disperser or the like is used. For example, a dispersion method. As a disperser, a homomixer, a homogenizer, a colloid mill, a line mixer, a bead mill, or the like can be used. Moreover, when carrying out aqueous dispersion, you may add a well-known organic solvent.

As described above, in the present invention, a two-component kit including a first agent containing an isocyanate-reactive hydrocarbon compound and a second agent containing an isocyanate compound is used, and the first agent and the second agent are used at the time of use. It is good also as a kit form which prepares the water repellent of this invention as water-based dispersion. Furthermore, in this invention, it is set as the 3 liquid type kit provided with the 1st agent containing an isocyanate-reactive hydrocarbon compound, the 2nd agent containing an isocyanate compound, and the 3rd agent containing an acrylic polymer, The agent, the second agent, and the third agent may be dispersed in water to form 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 in which a first agent and a second agent are dispersed in water, the isocyanate compound being a second agent for the functional group of the hydrocarbon compound of the first agent The molar ratio of the crosslinkable functional group is 0.3 or more.

The three-component type kit of the present invention includes 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 used as an aqueous dispersion, wherein the first agent, the second agent, and the third agent are dispersed in water. 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 of the present invention. Therefore, the kind and content of the isocyanate-reactive hydrocarbon compound, isocyanate compound, acrylic polymer, and other components are the same as the water repellent of the present invention described above. For example, in the case of a two-component type kit, at least one of the acrylic polymer and other components can be blended with the first agent and the second agent. For example, if it is a 3 liquid type kit, another component can be mix | blended with at least 1 of a 1st agent, a 2nd agent, and a 3rd 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 fiber product of the present invention is produced by bringing the water-repellent agent of the present invention into contact with the fiber product. The details of the water repellent of the present invention are as described above.

The fiber 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, wool, polyester, nylon, acrylic, Examples thereof include synthetic fibers such as spandex and fiber products using them. In addition, there are no restrictions on the form and shape of the textile product, and not only the shape of raw materials such as staples, filaments, tows, and yarns, but also various processes such as woven fabrics, knitted fabrics, stuffed cotton, non-woven fabrics, paper, sheets, and films. It may be in the form.

Moreover, the flame retardant treatment may be applied to the textile product in advance. For example, in the case of polyester, flame retardancy treatment can be performed by appropriately selecting from the above-mentioned flame retardants in consideration of compatibility with the yarn-making property. The treatment method using a flame retardant is not particularly limited, and may be mixed by a method of simply adding to a polymer or a method of copolymerizing with polyester at a molecular level.

Using the water repellent of the present invention, a water repellent treatment can be performed on a fiber product (cloth or the like) by a known method. Examples of the method for treating a fiber product with the water repellent of the present invention include a continuous method or a batch method. If the water repellent of the present invention is a stock solution, the concentration suitable for 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 processing liquid is prepared by diluting the water repellent with water so as to be approximately%.

As a continuous method, it is also preferable to optionally add various agents such as a cross-linking agent in addition to water when preparing the processing liquid. Next, an object to be processed (that is, a fiber product) is continuously fed into the impregnation apparatus filled with the processing liquid, and the processing object is impregnated with the processing liquid, and then the unnecessary processing liquid is removed. The impregnation device is not particularly limited, and a padder, a kiss roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator, etc. can be preferably employed, and a padder type is particularly preferable. Subsequently, an operation of removing water remaining on the object to be processed is performed using a dryer. The dryer is not particularly limited, and a spread dryer such as a hot fluid or a tenter is preferable. The continuous method is preferably employed when the object to be treated is a fabric such as a 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 on the object to be processed. The batch method is preferably employed when the object to be treated is not in the form of a fabric, for example, in the case of loose hair, top, sliver, skein, tow, yarn or the like, or when it is not suitable for continuous methods such as knitting. In the dipping step, for example, a cotton dyeing machine, a cheese dyeing machine, a liquid dyeing machine, an industrial washing machine, a beam dyeing machine or the like can be used. In the operation of removing water, a hot air dryer such as a cheese dryer, a beam dryer or a tumble dryer, a high-frequency dryer or the like can be used. It is preferable to perform a dry heat treatment on the workpiece to which the water repellent of the present invention is attached.

As 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. In particular, 160 to 180 ° C. is preferable. As the time for 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. For 10 seconds to 3 minutes, 10 seconds to 2 minutes, 1 to 3 minutes, and 1 to 2 minutes. The method for the dry heat treatment is not particularly limited, but a tenter is preferable when the object to be processed is in the form of a fabric.

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

<Synthesis of isocyanate-reactive hydrocarbon compound>
(Synthesis Example 1: Myo-inositol laurate)
To the flask, 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. The solution was heated to reflux and water was removed from the reaction 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 filtration was performed and the collected solid was dried in an oven under reduced pressure overnight. The obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 123.2 mgKOH / g.

(Synthesis Example 2: Myo-inositol stearate)
To the flask, 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 were added. The solution was heated to reflux and water was removed from the reaction 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 in a vacuum oven overnight. The obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 89.6 mgKOH / g.

(Synthesis Example 3: Mannitol behenate)
To the flask, 12 g (0.066 mol) of mannitol, 56 g (0.164 mol) of behenic acid, and 5.0 g of 10% by mass sodium hydroxide solution were added and 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 overnight in a vacuum oven. The obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 268.8 mgKOH / g.

(Synthesis Example 4: Xylitol behenate)
To the flask, 12 g (0.079 mol) of xylitol, 40.2 g (0.118 mol) of behenic acid, and 5.0 g of 10% by mass sodium hydroxide solution were added. 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 overnight in a vacuum oven. The obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 470.4 mgKOH / g.

(Synthesis Example 5: xylose palmitate)
To the flask, 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. The reaction was stirred at room temperature. 8.4 g of triethylamine 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 obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 179.2 mgKOH / g.

(Synthesis Example 6: glucose palmitate)
Glucose 5.0 g (0.028 mol), palmitic acid chloride 26.7 g (0.097 mol), and dichloromethane 70 g 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 obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 123.2 mgKOH / g.

(Synthesis Example 7: Tristearyl citrate)
To the flask, 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. The solution was heated to reflux and water was removed from the reaction using a Dean-Stark trap. After cooling to 0 ° C. to precipitate the product, it was filtered and recrystallized using ethanol. The solid was collected by filtration and dried overnight in a vacuum oven. The resulting isocyanate-reactive hydrocarbon compound had a hydroxyl value of 58.8 mgKOH / g.

(Synthesis Example 8: trimethylolpropane stearate)
A flask was charged with 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, and dehydrated at 140 to 210 ° C. for 3 hours under a nitrogen stream. Went. The resulting isocyanate-reactive hydrocarbon compound had a hydroxyl value of 84.0 mgKOH / g.

(Synthesis Example 9: Ditrimethylolpropane stearate)
A flask was charged with 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, and the mixture was kept at 120 to 180 ° C. for 5.5 hours under a nitrogen stream. A dehydration reaction was performed. The obtained isocyanate-reactive hydrocarbon compound had a hydroxyl value of 53.2 mgKOH / g.

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

<Preparation of aqueous dispersion of isocyanate-reactive hydrocarbon compound>
Emazole S-30V (sorbitan tristearate, manufactured by Kao Corporation), Riquemar B-150 (sorbitan tribehenate, manufactured by Riken Vitamin Co., Ltd.), and each isocyanate-reactive hydrocarbon compound obtained in Synthesis Examples 1 to 10 An aqueous dispersion of an isocyanate-reactive hydrocarbon compound was prepared by the following procedure using the composition shown in Table 1. To the flask, 20 g of an isocyanate-reactive hydrocarbon compound and 20 g of methyl isobutyl ketone were added and melted at 80 ° C. Stearylamine 30EO adduct 1.0 g and acetic acid (90% aqueous solution) 0.3 g were dissolved in 78.7 g of ion-exchanged water at 80 ° C. and added dropwise. The mixture was emulsified with a high-pressure homogenizer (400 bar) while maintaining the temperature. 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. Each average particle size was measured. The average particle diameter is a particle diameter (median particle diameter) having a percentage integrated value (volume basis) of 50% measured by a laser diffraction / scattering particle diameter distribution measuring apparatus LA-300 (manufactured by Horiba, Ltd.). (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) of duranate 24A-100 (biuret of hexamethylene diisocyanate, manufactured by Asahi Kasei Chemicals Corporation, NCO% = 23.5) and 65.9 g of methyl isobutyl ketone (MIBK). Started. Thereto, 53.8 g (0.560 mol) of 3,5-dimethylpyrazole was charged and held at 50 ° C., and reacted until the isocyanate content became zero to obtain a blocked isocyanate compound. 30.8 g of MIBK, 65.9 g of propylene glycol monomethyl ether, and 0.31 g of stearyltrimethylammonium chloride as a cationic surfactant were mixed to obtain a uniform solution. While gradually stirring, 175.8 g of ion-exchanged water was charged, and then 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 obtained aqueous dispersion contains 0.73 mmol / g of a crosslinkable functional group (block isocyanate group). The average particle size of this aqueous dispersion was 0.44 μm.

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

<Preparation of aqueous dispersion of acrylic polymer>
(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 ( 6. 69.0 g of 10% diluted aqueous solution of polyoxyethylene (EO: 26) oleyl ether, manufactured by Kao Corporation), 10% diluted aqueous solution of Arcard 18-63 (alkyl (C16-18) trimethylammonium chloride, manufactured by Lion Corporation) 8 g, 10% diluted aqueous solution of pronone 204 (ethylene oxide propylene oxide polymer (the proportion of ethylene oxide is 40% by mass), manufactured by NOF Corporation), 82.8 g of dipropylene glycol, 328.3 g of ion-exchanged water And 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 put in an autoclave and cooled to 30 ° C. or lower. Add 107.6 g of vinylidene chloride and 13.8 g of 10% diluted aqueous solution of VA-061 (2,2′-azobis [2- (2-imidazolin-2-yl) propane], manufactured by Wako Pure Chemical Industries, Ltd.) After replacing the gas phase with nitrogen, the polymerization reaction was carried out at 65 ° C. for 15 hours with stirring, and ion exchange 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 perfluoroalkyl group and a fluorine atom and a chlorine atom derived from vinylidene chloride.

(Production Example 16)
In an autoclave, 47.5 g of stearyl acrylate, 2.5 g of glycidyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 2 g of polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether, Dioctadecyldimethylammonium chloride (1.5 g) was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 3 hours. Ion exchange water was added to adjust the solid content concentration to 22% to obtain an aqueous dispersion of an acrylic polymer. The average particle size of this aqueous dispersion was 0.14 μm. The obtained acrylic polymer does not contain a halogen atom.

(Production Example 17)
Stearyl acrylate 20 g, lauryl acrylate 17.5 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) ) 2 g of ether and 1.5 g of dioctadecyldimethylammonium chloride were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After the atmosphere in the autoclave was replaced with nitrogen, 10 g of vinyl chloride was charged by injection, 0.5 g of 2,2-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was reacted at 60 ° C. for 3 hours. Ion exchange water was added to adjust the solid content concentration to 22% to obtain an aqueous dispersion of an 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)
94 g of stearyl acrylate, 4 g of KF-2012 (radical reactive organopolysiloxane macromonomer, manufactured by Shin-Etsu Chemical Co., Ltd.), 2 g of 2-hydroxyethyl methacrylate, 1 g of stearyltrimethylammonium chloride, 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 added and emulsified and dispersed at 50 ° C. by high-speed stirring. Then, it processed by the high pressure homogenizer (400 bar), keeping at 40 degreeC, and obtained the emulsion. To this emulsion, 0.3 g of azobis (isobutylamidine) dihydrochloride was added and reacted at 60 ° C. for 10 hours in a nitrogen atmosphere. Ion exchange water was added to adjust the solid content concentration to 21.8% to obtain an aqueous dispersion of an acrylic polymer. The average particle size of this aqueous dispersion was 0.18 μm. The resulting acrylic polymer is an acrylic-silicone polymer and does not contain 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 (Contains about 10% by mass of dimethacrylate), manufactured by Nippon Oil & Fats Co., Ltd.) 6.98 g, Pronon 204 (ethylene oxide propylene oxide polymer (the proportion of ethylene oxide is 40% by mass), manufactured by Nippon Oil & Fats Co., Ltd.) 3.1 g, NIKKOL AM-3130N (coconut oil fatty acid amidopropyl betaine solution, manufactured by Nippon Surfactant) 3.1 g, Emulgen E430 (polyoxyethylene (EO: 26) oleyl ether, manufactured by Kao Corporation) 10.8 g, water 434.2 g, dipropylene 104.8 g of glycol, and n Put dodecyl mercaptan 3.5 g, After warming for 60 minutes at 60 ° C., were pretreated with 100bar at a high pressure homogenizer to obtain an emulsion and the treatment with 400 bar. 714.8 g of the obtained emulsion was put in an autoclave, and 1.4 g of VA-061 (2,2′-azobis [2- (2-imidazolin-2-yl) propane], manufactured by Wako Pure Chemical Industries, Ltd.) was added. And cooled to 30 ° C. or lower. After replacing the gas phase with nitrogen and introducing 78.2 g of vinyl chloride, the polymerization reaction was carried out with stirring at 55 ° C. for 1 hour and at 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 perfluoroalkyl group and a fluorine atom and a chlorine atom derived from vinyl chloride.

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

<Evaluation of water repellency and flame retardancy>
As a test cloth, a PET tropical cloth (weighing 138 g / m ² , undyed, flame retardant untreated) was prepared. Next, using the water repellent as a processing liquid, the test cloth is passed through the processing liquid by a continuous method, and an unnecessary solution is squeezed with a mangle at a constant pressure, dried at 110 ° C. for 1.5 minutes, and 170 ° C. And cured for 1 minute to obtain a processed cloth. The pickup was 92%.

(Water repellency evaluation)
The obtained work cloth was evaluated in accordance with 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, “+” was assigned to the grade, and when the performance was slightly inferior, “−” was assigned to the grade. Also, the grade 3 or higher was accepted. The results are shown in Tables 2 and 3.
5: No wetting or water droplets on the surface 4: No wetting on the surface but showing small water droplets 3: Wetting on small individual water droplets on the surface 2: Wetting on half of the surface , With small individual wetness penetrating the fabric 1: showing wetness over the entire surface

(Flame retardance evaluation)
In accordance with the provisions of the FMVSS-302 method (horizontal method, ISO 3795), the processed fabric obtained above was evaluated for flame retardancy. The self-extinguishing (flame retardant) and self-extinguishing properties before the marked line were regarded as acceptable. Here, self-extinguishing before the marked line means that the test piece does not ignite or self-extinguishes before the A marked line, and self-extinguishing means self-extinguishing within a combustion 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 apparent 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 fibers, and the flame retardancy of the fibers was inhibited. It turns out that it is suppressed effectively. On the other hand, the water repellents of Comparative Examples 1 to 4 could not achieve both excellent water repellency and flame retardance inhibiting effect.

[Examples 19 to 26 and Comparative Examples 6 to 9]
<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 to 100% by mass with water so as to have the composition shown in Table 4. 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 acrylic polymer content (parts by mass) with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound. As Comparative Examples 7 and 8, 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), which are commercially available wax-based water repellents Agent; solid content concentration 34%; manufactured by Meisei Chemical Industry Co., Ltd.).

<Evaluation of water repellency and flame retardancy>
A PET tropical cloth (weighing 138 g / m ² , undyed, flame retardant untreated) was prepared. Next, the following flame retardant treatment was performed on the PET tropical cloth to obtain a test cloth.

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

Next, as a soaping step, exhaustion was performed using an aqueous solution containing Rakkor 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 performing hot water washing and water washing, it was dried at 110 ° C. for 2 minutes to obtain a test cloth subjected to flame retardant treatment.

Next, using the water repellent agent shown in Table 4 as the processing liquid, the test cloth was passed through the processing liquid in a continuous manner in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and a mangle with a constant pressure was used. The unnecessary solution was squeezed, dried at 110 ° C. for 1.5 minutes, and cured at 170 ° C. for 1 minute to obtain a processed cloth. The pickup was 92%.

(Water repellency evaluation)
The 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.

(Flame retardance evaluation)
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 contain an acrylic polymer, but, as in Example 19, which does not contain an acrylic polymer, excellent water repellency for fibers. Further, it is understood 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 unable to achieve both excellent water repellency and flame retardance inhibiting 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 to 100% by mass with water so as to have the composition shown in Table 5. 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 with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound. As Comparative Example 10, Paragit ZS (wax-zirconium-based water repellent; solid concentration 24%; manufactured by Meisei Chemical Co., Ltd.), which is a commercially available wax-based water repellent, was used. As Comparative Example 11, AsahiGuard E-SERIES AG-E550D (C6 fluorine-based water repellent; manufactured by Asahi Glass Co., Ltd.), which is a commercially available C6 fluorine-based water repellent, was used.

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

(Flame retardant treatment)
A mini color dyeing machine was used and the bath ratio was 1:20. Phoscon MK-PZ (brominated flame retardant; solid content concentration 48%; manufactured by Meisei Chemical Industry Co., Ltd., 20% owf), Disper FR-21N (dispersant; solid content concentration 77%; Meisei Chemical Industry Co., Ltd.) Manufactured by 2.0% o.w.) and an aqueous solution containing acetic acid (90% aqueous solution; 0.3 g / L), a PET shower curtain was exhausted at 130 ° C. for 30 minutes.

Next, as a soaping process, Unisort 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) A PET shower curtain subjected to exhaustion treatment using an aqueous solution containing 2.0 g / L) and soda ash (2.0 g / L) was washed at 80 ° C. for 15 minutes. After performing hot water washing and water washing, it was dried at 110 ° C. for 2 minutes to obtain a test cloth.

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

(Water repellency evaluation)
The 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, the state of whether or not water has oozed out on the back surface of the test cloth after the spray test is visually observed. Was evaluated as x. The results are shown in Table 5.

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

As is apparent from the results shown in Table 5, the water repellents of Examples 27 to 31 impart excellent water repellency to the fibers, and further, the inhibition of the flame retardancy of the fibers is effectively suppressed. I understand that. In contrast, the water repellents of Comparative Examples 10 to 11 were unable to achieve both excellent water repellency and flame retardance inhibiting effect.

[Example 32 and Comparative Examples 13 to 15]
<Preparation of water repellent>
100% by mass of an aqueous dispersion of an isocyanate-reactive hydrocarbon compound, an aqueous dispersion of an isocyanate compound, an aqueous dispersion of an acrylic polymer, and a phosphorus flame retardant together with water so as to have the composition shown in Table 6. A water repellent was prepared by diluting and mixing. 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. 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 a phosphorus flame retardant, K-19A (phosphorus flame retardant; solid content concentration: 100%; manufactured by Meisei Chemical Industry Co., Ltd.) was used. 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 flame retardant were used in combination.

<Evaluation of water repellency and flame retardancy>
Nylon high-density taffeta (weighing 60 g / m ² , dyed, flame retardant untreated (treated with a phosphorus flame retardant when treated with a water repellent)) was prepared as a test cloth. Next, using the water repellent of Table 6 as the processing liquid, the test cloth was passed through the processing liquid by a continuous method, and unnecessary solution was squeezed with a mangle at a constant pressure, and dried at 110 ° C. for 1.5 minutes, 170 A processed cloth was obtained by curing at 0 ° C. for 1 minute. The pickup was 42%.

(Water repellency evaluation)
The 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.

(Flame retardance evaluation)
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, the 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 were unable to achieve both excellent water repellency and flame retardancy inhibiting effect.

[Examples 33 to 34]
<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 to 100% by mass with water so as to have the composition shown in Table 7. 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 acrylic polymer content (parts by mass) with respect to 100 parts by mass in total of the hydrocarbon compound and the isocyanate compound.

<Evaluation of water repellency and flame retardancy>
A PET tropical cloth (weighing 138 g / m ² , undyed, flame retardant untreated) was prepared. Next, the following flame retardant treatment was performed on the PET tropical cloth to obtain a test cloth.

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

Next, as a soaping step, exhaustion was performed using an aqueous solution containing Rakkor 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 performing hot water washing and water washing, it was dried at 110 ° C. for 2 minutes to obtain a test cloth subjected to flame retardant treatment.

Next, using the water-repellent agent shown in Table 7 as the working fluid, the test cloth was passed through the working fluid in a continuous manner in the same manner as in Examples 1 to 18 and Comparative Examples 1 to 5, and then with a mangle of constant pressure. The unnecessary solution was squeezed, dried at 110 ° C. for 1.5 minutes, and cured at 170 ° C. for 1 minute to obtain a processed cloth. The pickup was 92%.

(Water repellency evaluation)
The 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.

(Flame retardance evaluation)
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)

1. At least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group, and an aqueous dispersion in which the isocyanate compound is 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.
2. 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 General Formula (1), W is an (a + b) -valent organic group. A is bonded to W and is —X—Y— or —Y—. B is bonded to W and is —XZ or —Z. a is an integer of 1 or more. b is an integer of 1 or more. (A + b) is 3 to 8. X is a divalent polyalkylene ether group. Y is a divalent group, and is an ether group, an ester group, an amide group, a urethane group, a urea group, or a thiourethane group. R is a straight-chain 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 -XZ, Z is a hydroxy group. ]
3. The water repellent according to claim 1 or 2, wherein the isocyanate compound is a blocked isocyanate.
4. The water repellent according to any one of claims 1 to 3, further comprising a surfactant.
5. The water repellent according to any one of claims 1 to 4, further comprising an acrylic polymer.
6. The water repellent according to claim 5, wherein the content of the acrylic polymer is 0.1 to 99 parts by mass with respect to a total of 100 parts by mass of the hydrocarbon compound and the isocyanate compound in the water repellent. .
7. The water repellent according to claim 5 or 6, wherein the acrylic polymer is an acrylic polymer containing a halogen element.
8. The water repellent according to any one of claims 5 to 7, wherein the acrylic polymer is an acrylic polymer containing no fluorine atom.
9. The water repellent according to claim 5 or 6, wherein the acrylic polymer is an acrylic polymer containing no halogen element.
10. The water repellent according to any one of claims 5 to 9, wherein the acrylic polymer is an acrylic-silicone polymer.
11. A water-repellent fiber product, which is treated with the water-repellent agent according to any one of claims 1 to 10.
12. 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.
13. A first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
    A second agent containing at least an isocyanate compound;
    With
    A kit for preparing a water repellent used as an aqueous dispersion in which the first agent and the second agent are dispersed in water,
    The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st agent is 0.3 or more.
14. A first agent comprising at least a hydrocarbon compound having a functional group capable of reacting with an isocyanate group;
    A second agent containing at least an isocyanate compound;
    At least a third agent comprising an acrylic polymer;
    With
    A kit for preparing a water repellent used as an aqueous dispersion in which the first agent, the second agent, and the third agent are dispersed in water,
    The kit whose molar ratio of the crosslinkable functional group of the said isocyanate compound of the said 2nd agent with respect to the functional group of the said hydrocarbon compound of the said 1st agent is 0.3 or more.