JP6863706B2 - Method for manufacturing water repellent composition, water repellent fiber product and water repellent fiber product - Google Patents

Description

The present invention relates to a water repellent composition capable of exhibiting excellent water repellency, a water repellent fiber product using the water repellent composition, and a method for producing a water repellent fiber product.

Conventionally, textile products to which a fluorine-based water repellent having a fluorine-containing group is attached are widely used because they exhibit high water repellency. On the other hand, there are concerns about the accumulation of fluorine-based compounds in the human body, and many developments of water-repellent materials using non-fluorine-based compounds are seen.

Conventionally, paraffin wax, silicone resin and the like are well known as water repellent compositions containing no fluorine compound, but the water repellency is inferior to that of the fluorine compound. Among these, in recent years, as a technique for using a composition containing no fluorine-based compound, it has been proposed that water repellency can be obtained by treating a composition containing a reagent that provides a surface effect and a polymer extender composition. ing. Here, the polymer extender composition is a urethane compound having an alkyl group, and a certain degree of water repellency can be obtained with this composition alone (Patent Document 1). Further, Patent Document 2 proposes that a composition containing an organic urethane compound has durable water repellency.

However, although these compositions have water repellency, it is difficult to easily obtain an aqueous dispersion having a small particle size, the stability over time is poor, and a uniform liquid cannot be maintained. Therefore, the water repellency decreases due to diurnal changes.

Special Table 2016-522330 Special Table 2016-524628

An object of the present invention is to provide a water-repellent composition, a water-repellent fiber product, and a water-repellent fiber product, which exhibit sufficient water repellency when attached to a fiber material and can suppress a decrease in water repellency due to aging. To provide a manufacturing method.

As a result of diligent studies to solve the above problems, the present inventors have found that a water repellent composition containing a specific urethane compound can solve the above problems, and arrived at the present invention.
That is, the water repellent composition of the present invention contains a urethane compound having a structural unit (a) derived from the organic polyisocyanate compound (A) and a structural unit (b) derived from the active hydrogen group-containing compound (B). , The structural unit (b1) derived from the polyol (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule and the active hydrogen group-containing compound (B2) having a carboxyl group. comprises only structural units derived from (b2), the said urethane compound, in water, emulsifying or dispersing it in, the particle diameter of the urethane compound is the 0.1～6Myuemu, the entire structural unit (b) The proportion of the constituent unit (b1) is 60 to 99.9 mol%, and the proportion of the constituent unit (b2) is 0.1 to 40 mol%.

The molar ratio (a: b) of the structural unit (a) to the structural unit (b) is preferably 1: 8 to 2: 1.

The ratio of the structural unit (b1) to the entire structural unit (b) is 60 to 99.9 mol%, and the ratio of the structural unit (b2) is 0.1 to 40 mol% .

The polyol (B1) is preferably a compound having 2 to 5 active hydrogen groups in the molecule and 1 to 5 hydrocarbon groups having 12 or more carbon atoms.

The active hydrogen group-containing compound (B2) is preferably at least one selected from 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid.

The urethane compound is dissolved, emulsified or dispersed.

The water-repellent fiber product of the present invention is obtained by treating a fiber material with the above-mentioned water-repellent composition.

The method for producing a water-repellent fiber product of the present invention includes a step of treating a fiber material with a treatment liquid containing the above-mentioned water-repellent composition.

The water repellent composition of the present invention is excellent in water repellency when attached to a fiber material. Furthermore, it is possible to suppress a decrease in water repellency due to diurnal changes.
The water-repellent fiber product of the present invention is excellent in water repellency. According to the method for producing a water-repellent fiber product of the present invention, a water-repellent fiber product having excellent water repellency can be obtained.

The present invention is a water repellent composition containing a specific urethane compound. This will be described in detail below.

[Urethane compound]
The urethane compound is an essential component of the water repellent composition of the present invention. The urethane compound is obtained by reacting the organic polyisocyanate compound (A) with the active hydrogen group-containing compound (B), and is obtained by reacting the organic polyisocyanate compound (A) with the structural unit (a) derived from the organic polyisocyanate compound (A) and the active hydrogen group-containing compound ( It has a structural unit (b) derived from B). Only one type of urethane compound may be used, or two or more types may be used.

(Organic polyisocyanate compound (A))
The organic polyisocyanate compound (A) is an essential constituent component of the urethane compound and contains two or more isocyanate groups in the molecule. The number of isocyanate groups in the molecule is preferably 2 to 4, more preferably 2 to 3. As the organic polyisocyanate compound (A), only one kind may be used, or two or more kinds may be used. Here, the structural unit derived from the organic polyisocyanate compound (A) means a unit composed of the organic polyisocyanate compound (A) as a raw material, and is of "-NHC (= O)-" in the urethane bond. Including up to the structure.

Examples of the organic polyisocyanate compound (A) include an aromatic polyisocyanate (A1) having 8 to 26 carbon atoms, an aliphatic polyisocyanate (A2) having 4 to 22 carbon atoms, and an alicyclic polyisocyanate compound (A2) having 8 to 18 carbon atoms. Examples thereof include A3), aromatic aliphatic polyisocyanates (A4) having 10 to 18 carbon atoms, and modified products (A5) of these polyisocyanates.

Examples of the aromatic polyisocyanate (A1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is referred to as TDI). (Omitted), crude TDI, 4,4'-or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4'-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenyl Examples thereof include methanetriisocyanate and m- or p-isocyanatophenylsulfonylisocyanate.

Examples of the aliphatic polyisocyanate (A2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecantryisocyanate, and 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-Diisocyanatohexanoate can be mentioned.

Examples of the alicyclic polyisocyanate (A3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Cyclohexylene diisocyanates, bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornan diisocyanates can be mentioned.

Examples of the aromatic aliphatic polyisocyanate (A4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

The modified product (A5) of the polyisocyanate compounds (A1) to (A4) includes a urethane group, a carbodiimide group, an alohanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group or an oxazolidone group in the molecule. Examples thereof include modified products of the polyisocyanates (A1) to (A4) contained therein. Examples of the modified product (A5) include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. ..

Among these organic polyisocyanate compounds (A), from the viewpoint of water repellency, aromatic polyisocyanates (A1) having 8 to 26 carbon atoms and aliphatic polyisocyanates (A2) having 4 to 22 carbon atoms are preferable, and 4 carbon atoms are preferable. The aliphatic polyisocyanate (A2) of ~ 22 is more preferable, and HDI is particularly preferable.

(The active hydrogen group-containing compound (B))
The active hydrogen group-containing compound (B) is an essential component of the urethane compound and refers to a compound having at least one active hydrogen group in the molecule. The active hydrogen group refers to an active group containing hydrogen that can react with an isocyanate group. Examples of the active hydrogen group include a hydroxyl group, an amino group, a carboxyl group, and a thiol group. Here, the structural unit (b) derived from the active hydrogen group-containing compound (B) means a unit composed of the active hydrogen group-containing compound (B) as a raw material, and is active from the active hydrogen group-containing compound (B). The balance excluding hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (A)).

The structural unit (b) derived from the active hydrogen group-containing compound (B) includes a structural unit (b1) and a carboxyl group derived from a polyol (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule. It contains a structural unit (b2) derived from the active hydrogen group-containing compound (B2). That is, the urethane compound includes an organic polyisocyanate compound (A), a polyol (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule, and an active hydrogen group-containing compound (B2) having a carboxyl group. It becomes a reaction product with the active hydrogen group-containing compound (B). The active hydrogen group-containing compound (B) may contain other active hydrogen group-containing compounds other than the polyol (B1) and the active hydrogen group-containing compound (B2) as long as the present invention is not impaired.

(Polycarbonate (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule)
The polyol (B1) is a compound having at least one hydrocarbon group having 12 or more carbon atoms in the molecule and at least one active hydrogen group. As the polyol (B1), only one kind may be used, or two or more kinds may be used.
The number of the hydrocarbon groups in the molecule is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3. The number of active water groups in the molecule is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3.

Examples of the hydrocarbon group of the polyol (B1) include an alkyl group and an alkenyl group. The hydrocarbon group may have a linear structure or a branched structure, and may be saturated or unsaturated. The hydrocarbon group has 12 or more carbon atoms, preferably 12 to 26, more preferably 14 to 22, and even more preferably 18 to 22. If the number of carbon atoms is less than 12, water repellency may be poor.

The polyol (B1) is not particularly limited as long as it satisfies the above conditions, but is preferably the following compound (B1-1) from the viewpoint of further exerting the effects of the present invention. That is, the structural unit (b1) is preferably a structural unit (b1-1) derived from the compound (B1-1).

A compound (B1-1) having a structure in which a fatty acid having 12 or more carbon atoms and a polyhydric alcohol having 3 or more valences are ester-bonded and having 2 or more hydroxyl groups in the molecule.
The fatty acid may have a linear structure or a branched structure, and may be saturated or unsaturated. The carbon number of the fatty acid is preferably 12 to 26, more preferably 14 to 22, and even more preferably 18 to 22.

Fatty acids include lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitreic acid, isosecylic acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vacene acid, linoleic acid, linolenic acid, Examples thereof include tubercrostearic acid, arachidic acid, isoeicosic acid, gadrainic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosanoic acid, nervonic acid, serotic acid, montanic acid, melicic acid and the like. Among these, myristic acid, palmitic acid, stearic acid, isostearic acid, and behenic acid are preferable, and stearic acid and behenic acid are more preferable.

Examples of trihydric or higher polyhydric alcohols include glycerin, sorbitol, sorbitol, pentaerythritol, alditol, trimethylolpropane, diglycerin, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, sucrose, and castor oil. , Hardened castor oil and alkylene oxide adducts thereof and the like. Among these, glycerin, sorbitol and pentaerythritol are preferable, and sorbitol and pentaerythritol are more preferable.

The number of ester bonds of compound (B1-1) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 to 3. The number of active water groups in the molecule of compound (B1-1) is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 to 3.

Examples of the compound (B1-1) include sorbitan tristearate, sorbitan distearate, sorbitan monostearate, glycerin distearate, glycerin dibenate, and distearyl erythritol. Among these, sorbitan tristearate, sorbitan distearate, sorbitan monostearate, and distearyl erythritol are preferable, sorbitan tristearate, sorbitan distearate, and distearyl erythritol are more preferable, and sorbitan distearate and distearyl erythritol are more preferable. Is even more preferable.
The method for producing the compound (B1-1) is not particularly limited, and a known method can be adopted.

Preferred compounds (B1) include sorbitol-type polyols represented by the following general formula (1) and erythritol-type polyols represented by the following general formula (2).

In formula (1), R ¹ , R ² , R ³ , and R ⁴ are independently hydrogen atoms or organic groups having 12 or more carbon atoms, and are R ¹ , R ² , R ³ , and R ^{4 respectively.} Of these, at least two are hydrogen atoms and at least one is an organic group having 12 or more carbon atoms. Of R ¹ , R ² , R ³ , and R ⁴ , it is preferable that two are hydrogen atoms and two are organic groups having 12 or more carbon atoms.

In the formula (2), R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently hydrogen atoms or organic groups having 12 or more carbon atoms, and are R ⁵ , R ⁶ , R ⁷ , and R 5, respectively. among R ^8, at least two are hydrogen atom, in which at least one of 12 or more organic groups carbon. Of R ⁵ , R ⁶ , R ⁷ , and R ⁸ , it is preferable that two are hydrogen atoms and two are organic groups having 12 or more carbon atoms.

Examples of the organic group having 12 or more carbon atoms include a hydrocarbon group having 12 or more carbon atoms and an acyl group having 12 or more carbon atoms, and an acyl group having 12 or more carbon atoms is preferable. The hydrocarbon group may have a linear structure or a branched structure, and may be saturated or unsaturated. The acyl group is a residue obtained by removing the OH group from the above-mentioned fatty acid having 12 or more carbon atoms. The preferred range of fatty acids and the like are the same as described above. The hydrocarbon group and the acyl group have preferably 12 to 26 carbon atoms, more preferably 14 to 22 carbon atoms, and even more preferably 18 to 22 carbon atoms.

The structural unit (b1) derived from the compound (B1) refers to the balance obtained by removing active hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (A)) from the compound (B1), and is the general formula described above. Taking the erythritol-type polyol represented by (2) as an example, it is a structural unit represented by any of the following general formulas (3), (4), and (5).

In the general formula (3), R ⁵ , R ⁶ , and R ⁷ are independently hydrogen atoms or organic groups having 12 or more carbon atoms, and at least one of ^{R 5} , R ⁶ , and R ^{7 is carbon.} It is an organic group of several 12 or more.

In the general formula (4), R ⁵ and R ⁷ are independently hydrogen atoms or organic groups having 12 or more carbon atoms ^{, and at least one of R 5} and R ⁷ is an organic group having 12 or more carbon atoms. Is.

In the general formula (5), R ⁷ is an organic group having 12 or more carbon atoms.

(Active hydrogen group-containing compound having a carboxyl group (B2))
Examples of the active hydrogen group-containing compound (B2) having a carboxyl group include a polyol having a carboxyl group and a monool having a carboxyl group. As the active hydrogen group-containing compound (B2), only one kind may be used, or two or more kinds may be used.
Examples of the polyol having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2-dimethylolheptanic acid, and dioxymaleic acid. , 2,6-Dioxybenzoic acid and the like.
Examples of monool having a carboxyl group include glycolic acid, lactic acid, hydroxybutyric acid, salicylic acid, parahydroxybenzoic acid, coumaric acid and the like.
Among these, a polyol having a carboxyl group is preferable from the viewpoint that many carboxyl groups can be introduced into the urethane compound and the stability of the obtained emulsion is good, and further, 2,2-dimethylolpropionic acid and 2,2. -Preferably at least one selected from dimethylolbutanoic acid.

The active hydrogen group-containing compound (B2) having a carboxyl group is preferably a compound represented by the following general formula (6).

In the general formula (6), R ⁹ is a hydrogen atom, an alkyl group or an alkenyl group. The alkyl group or alkenyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms. More preferably, it is 1 to 10.
M is a hydrogen atom, an alkali metal, an alkaline earth metal or ^a group represented by ^{NR a R b} R ^c R ^d . Among these, M is ^{preferably a hydrogen atom, an alkali metal or NR a} R ^b R ^c R ^{d, and} more preferably a hydrogen atom or an alkali metal.

Examples of the alkali metal include lithium, sodium, potassium and the like. Examples of the alkaline earth metal include magnesium, calcium, barium and the like.

R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. The number of carbon atoms of the alkyl group is preferably 1 to 30, and more preferably 1 to 10. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like. The alkanol group preferably has 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of such an alkanol group include a methanol group, an ethanol group, an n-propanol group, an isopropanol group and the like. The polyoxyalkylene group preferably has 2 to 4 carbon atoms. Examples of such a polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.

The structural unit (b2) derived from the compound (B2) refers to the balance obtained by removing active hydrogen (active hydrogen that contributes to the reaction with the organic polyisocyanate compound (A)) from the compound (B2), and is the general formula described above. Taking the compound represented by (6) as an example, it is a structural unit represented by the following general formula (7).

(Other active hydrogen group-containing compounds (B3))
The active hydrogen group-containing compound (B) may contain an active hydrogen group-containing compound (B3) other than the above-mentioned polyol (B1) and active hydrogen group-containing compound (B2) as long as the effects of the present invention are not impaired. Good. In other words, the structural unit (b) may include a structural unit (b3) derived from the active hydrogen group-containing compound (B3) other than the polyol (B1) and the active hydrogen group-containing compound (B2).

Examples of the active hydrogen group-containing compound (B3) include monool components such as methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol, nonanol, phenol, and benzyl alcohol; ethylene glycol, diethylene glycol, trimethylolethylene glycol, polyethylene glycol, and propylene. Glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neo Diol components such as pentyl glycol, tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, resorcin, hydroquinone, bisphenol A or an alkylene oxide adduct thereof; trimethylolethane, trimethylolpropane, glycerin, sorbitol , Pentaerythritol, trimethylolpropane and other trifunctional polyols; monoamines such as laurylamine, myristylamine, palmitylamine and stearylamine; trifunctional or higher such as melamine, diethylenetriamine, triethylenetetramine and tri (aminomethyl) propane. Polyamine and the like.

The ratio of the structural unit (b1) derived from the polyol (B1) to the total structural unit (b) derived from the active hydrogen group-containing compound (B) is preferably 60 to 99.9 mol%, more preferably 64 to 64 to It is 97 mol%, more preferably 67-93 mol%, and particularly preferably 70-90 mol%. If the ratio is less than 60 mol%, water repellency may not be sufficiently developed. On the other hand, when the ratio exceeds 90 mol%, the emulsion stability may be lowered, and the water repellency may be lowered due to diurnal change.

The ratio of the structural unit (b2) derived from the active hydrogen group-containing compound (B2) to the total structural unit (b) is preferably 0.1 to 40 mol%, more preferably 0.5 to 36 mol%, and further. It is preferably 1 to 33 mol%, particularly preferably 2 to 30 mol%. If the ratio is less than 0.1 mol%, the emulsion stability may be lowered, and the water repellency may be lowered due to diurnal change. On the other hand, when the ratio exceeds 40 mol%, water repellency may not be sufficiently developed.

The total ratio of the structural unit (b1) and the structural unit (b2) to the entire structural unit (b) is preferably 80 to 100 mol%, more preferably 82 to 99.5 mol%, and further preferably 85 to 85. It is 99 mol%, particularly preferably 88-98 mol%. If the ratio is less than 80 mol%, water repellency may not be sufficiently developed.

When the other active hydrogen group-containing compound (B3) is contained, the ratio of the structural unit (b3) derived from the active hydrogen group-containing compound (B3) to the total structural unit (b) is preferably 0 to 20 mol%. It is more preferably 0.5 to 18 mol%, further preferably 1 to 15 mol%, and particularly preferably 2 to 12 mol%. If the ratio exceeds 20 mol%, water repellency may not be sufficiently developed.

In the urethane compound, the molar ratio (a: b) of the structural unit (a) derived from the organic polyisocyanate compound (A) to the structural unit (b) of the active hydrogen group-containing compound (B) is preferably 1: 8. It is ~ 2: 1, more preferably 3: 5 to 3: 2, and even more preferably 4: 5 to 1: 1. If the molar ratio is not in the range of 1: 8 to 2: 1, the molecular weight of the urethane compound is low, so that the expression of water repellency may be insufficient.
The molar ratio of the structural unit (a) to the structural unit (b) is the molar ratio of the active hydrogen group-containing compound (A) and the organic polyisocyanate compound (B) when producing the urethane compound.

When the combined ratio of the organic polyisocyanate compound (A) and the active hydrogen group-containing compound (B) is 100 mol%, the ratio of the active hydrogen group-containing compound (B) is preferably 10 to 90 mol%. .. If the molar ratio of the active hydrogen group-containing compound (B) is less than 10, water repellency may be insufficient. The ratio is preferably 20 to 80 mol%, more preferably 25 to 75 mol%, still more preferably 30 to 70 mol%.

The weight average molecular weight of the urethane compound is preferably 4,000 to 2,000,000, more preferably 6,000 to 1,000,000, and even more preferably 8,000 to 500,000. If the molecular weight is less than 4,000, sufficient water repellency may not be exhibited. On the other hand, when the molecular weight exceeds 2,000,000, the emulsion stability may be lowered, and the water repellency may be lowered due to diurnal change.

The degree of polymerization of the urethane compound is preferably 4 to 2,000, more preferably 6 to 1,000, and even more preferably 8 to 500. If the degree of polymerization is less than 4, sufficient water repellency may not be exhibited. On the other hand, when the degree of polymerization exceeds 2,000, the emulsion stability may be lowered, and the water repellency may be lowered due to diurnal change.

The hydroxyl value of the urethane compound is preferably 0 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g, and even more preferably 10 to 80 mgKOH / g. The hydroxyl value was measured in accordance with JIS K 1557-1970.

The method for producing the urethane compound is not particularly limited, and a known method can be adopted. For example, a one-shot method in which all the components are reacted at the same time, a multi-stage method in which the active hydrogen group-containing compound (B) is stepwise charged and reacted with the organic polyisocyanate compound (A), or an active hydrogen group-containing compound (B). ) And the organic polyisocyanate compound (A) to synthesize a prepolymer having an isocyanate at the terminal, and then a chain extender is reacted with the prepolymer method.

Examples of the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazin, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 3,3'. -Dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, -hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylamino Propylamine, ethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, dihydrazide succinate, dihydrazide adipic acid, dihydrazide glutarate, dihydrazide sebacate, isophthal Chain extenders with amino groups such as acid dihydrazide, β-semicarbazide propionate hydrazide, 3-semicarbazide-propyl-carbazic acid ester, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane; ethylene Glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, 4, Chain extenders having a hydroxyl group such as 4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone, and trimethylpropane can be used. These chain extenders may be used alone or in combination of two or more.

When preparing the urethane compound, a urethanization catalyst can be used if necessary. Examples of the urethanization catalyst that can be used in the present invention include nitrogen-containing compounds such as triethylamine, triethylenediamine, or N-methylmorpholine, metal salts such as potassium acetate, zinc stearate, and tin octylate, and dibutyllaurate. Organic metal compounds and the like.

[Water repellent composition]
The water repellent composition of the present invention essentially contains the above urethane compound. By containing such a urethane compound, sufficient water repellency can be exhibited when it is attached to the fiber material, and further, a decrease in water repellency due to diurnal change can be suppressed.
The water-repellent composition of the present invention repels water when it is composed only of a component that exerts a water-repellent function (hereinafter referred to as a water-repellent component) such as the above-mentioned urethane compound or a fluorine-based water repellent having a fluorine atom in the molecule. The concept includes the case where a water component and other components are contained, and the case where the water repellent component is dissolved, emulsified or dispersed in water and / or an organic solvent. The water repellent composition of the present invention preferably contains substantially no fluorine-based water repellent (non-fluorine-based water repellent composition), but is not limited thereto.

In the water repellent composition of the present invention, it is preferable that the urethane compound is dissolved, emulsified or dispersed in water. The weight ratio of the urethane compound to the non-volatile content of the water repellent composition (dissolved product, dispersion or emulsion) is preferably 10 to 90% by weight, more preferably 15 to 80% by weight, still more preferably 20 to 70. By weight%. Here, the non-volatile content (also referred to as solid content) means that a certain amount of a sample is spread flat on an aluminum sheet and dried at 110 ° C. under irradiation with an infrared lamp, and the fluctuation range of the volatile content for 150 seconds becomes 0.15% by weight. This is the balance when the end point of the measurement is the time when it becomes.

When the urethane compound is emulsified and dispersed in water, the particle size of the urethane compound has a median value (median value) of preferably 0.01 to 8 μm, more preferably 0.05 to 7 μm, and further preferably 0. It is 10 to 6 μm. In the present invention, the median value (median value) means the median value (median value) of the particle size based on the volume.

When the urethane compound is dissolved, emulsified or dispersed in water and / or an organic solvent, it is preferable to use a surfactant. The proportion of the surfactant is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, still more preferably 10 to 20% by weight, based on the urethane compound.

Suitable surfactants are mainly nonionic surfactants, but may also contain cationic surfactants and anionic surfactants. The surfactant may be used alone or in combination of two or more.

Examples of the nonionic surfactant include polyoxyalkylene linear alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether; Polyoxyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isostearyl ether; polyoxyethylene 1-hexylhexyl ether, polyoxyethylene 1-octylhexyl ether , Polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pentyl ether and other polyoxyalkylene branched secondary alkyl ethers; polyoxyethylene oleyl ether and the like. Alkylene alkenyl ether; polyoxyalkylene alkyl phenyl ether such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether; polyoxyethylene tristyryl phenyl ether, polyoxyethylene distyryl phenyl ether, poly Polyoxyalkylene alkylarylphenyl ethers such as oxyethylene styrylphenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene benzyl phenyl ether; polyoxyethylene monolaurate, polyoxyethylene monooleate , Polyoxyethylene monostearate, polyoxyethylene monomyristylate, polyoxyethylene dilaurate, polyoxyethylene diolate, polyoxyethylene dimyristylate, polyoxyalkylene fatty acid esters such as polyoxyethylene distearate; sorbitan Solbitan esters such as monopalmitate and sorbitan monoolate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin monostearate, glycerin monolaurate, glycerin monopalmitate and the like. Glycerin fatty acid ester; polyoxyalkylene sorbitol fatty acid ester; sucrose fat Acid ester; Polyoxyalkylene castor oil ether such as polyoxyethylene castor oil ether; Polyoxyalkylene cured castor oil ether such as polyoxyethylene cured castor oil ether; Polyoxyalkylene alkyl such as polyoxyethylene laurylamino ether and polyoxyethylene stearylamino ether. Amino ether; oxyethylene-oxypropylene block or random copolymer; terminal alkyl ether of oxyethylene-oxypropylene block or random copolymer; terminal sucrose ether of oxyethylene-oxypropylene block or random copolymer; Etc. can be mentioned.

Examples of the anionic surfactant include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; hydroxyacetic acid, potassium hydroxyacetate, lactic acid, and lactic acid. Phosphonate-containing carboxylic acid (salt) such as potassium salt; polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); Salts of substituted aromatic compounds; alkylbenzene sulfonic acids (salts) such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acids (salts) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); Higher fatty acids amide sulfonic acids (salts) such as stearoylmethyl taurine (sodium), lauroyl methyl taurine (sodium), myristoyl methyl taurine (sodium), palmitoyl methyl taurine (sodium); N-acylsarcosine such as lauroyl sarcosic acid (sodium) Acid (salt); alkylphosphonic acid (salt) such as octylphosphonate (potassium salt); aromatic phosphonic acid (salt) such as phenylphosphonate (potassium salt); 2-ethylhexylphosphonate mono2-ethylhexyl ester (potassium salt), etc. Alkylphosphonic acid alkylphosphoric acid ester (salt); nitrogen-containing alkylphosphonic acid (salt) such as aminoethylphosphonic acid (diethanolamine salt); alkylsulfate ester (salt) such as 2-ethylhexyl sulfate (sodium salt); polyoxy Polyoxyalkylene sulfate esters (salts) such as ethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as di-2-ethylhexyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium N-lauroyl glutamate, N- Long-chain N-acylglutamates such as stearoyl-L-disodium glutamate; and the like.

Examples of the cationic surfactant include lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, and coconut oil alkyltrimethyl. Ammonium chloride, beef fat alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methsulfate, oleyldimethylethylammonium etosulfate, dioctyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride , Octadecyl diethylmethylammonium sulfate, etc. Alkyl quaternary ammonium salts; (polyoxyethylene) laurylaminoether emulsion, stearylaminoether emulsion, di (polyoxyethylene) laurylmethylaminoether dimethyl phosphate, di (polyoxyethylene) (Polyoxyalkylene) such as (ethylene) lauryl ethylammonium etosulfate, di (polyoxyethylene) hardened beef alkylethylamine etosulfate, di (polyoxyethylene) laurylmethylammonium dimethyl phosphate, di (polyoxyethylene) stearylamine lactate, etc. Alkylaminoether salt; acyls such as N- (2-hydroxyethyl) -N, N-dimethyl-N-stearoylamide propylammonium nitrate, lanolin fatty acid amidopropylethyldimethylammonium etosulfate, lauroylamide ethylmethyldiethylammonium metosulfate, etc. Amidoalkyl quaternary ammonium salts; alkylethenoxy quaternary ammonium salts such as dipalmitylpolyethenoxyethylammonium chloride, distearylpolyethenoxymethylammonium chloride; alkylisoquinolinium such as laurylisoquinolinium chloride. Salt; benzalconium salt such as lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride; benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutylfe) Nooxy) etoxy] ethyl} benzethonium salts such as ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts such as oleylhydroxyethyl imidazolinium etosulfate and laurylhydroxyethyl imidazolinium etosulfate; N-cocoylarginine ethyl Acylbasic amino acid alkyl ester salts such as ester pyrrolidone carboxylate and N-lauroyl lysine ethyl ethyl ester chloride; primary amine salts such as lauryl amine chloride, stearyl amine bromide, cured beef alkylamine chloride, rosinamine acetate; cetyl Secondary amine salts such as methylamine sulfate, laurylmethylamine chloride, dilaurylamine acetate, stearylethylamine bromide, laurylpropylamine acetate, dioctylamine chloride, octadecylethylamine hydroxide; dilaurylmethylamine sulfate, lauryldiethylamine chloride , Lauryl ethyl methylamine bromide, diethanol stearylamide ethylamine trihydroxyethyl phosphate salt, stearylamide ethylethanolamine urea polycondensate acetate and other tertiary amine salts; fatty acid amide guanidinium salt; lauryltriethylene glycol ammonium hydrooxide Alkyltrialkylene glycol ammonium salt and the like.

The water may be pure water, distilled water, purified water, soft water, ion-exchanged water, tap water, or the like.
Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone. A solvent, an aromatic-containing solvent such as toluene or xylene, or the like can be used. These organic solvents may be used alone or in combination of two or more.

The water repellent composition of the present invention may contain other components other than the above components as long as the effects of the present invention are not impaired. Other ingredients include discoloration inhibitors, antibacterial agents, fungicides, insect repellents, mite repellents, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, antifouling agents, and deepening. Examples thereof include post-processing agents for fibers such as agents, smoothing agents, softeners or water absorbents, oil agents, surfactants, inorganic substances, preservatives, pH adjusters, antifoaming agents, solvents, fatty acids (salts) and the like.

The method for producing the water repellent composition of the present invention is not particularly limited, and a known method can be adopted. For example, it can be obtained by mixing the urethane compound, surfactant, and water obtained by the above method and emulsifying them using a general stirrer and an emulsifier such as a homomixer, a homogenizer, a colloid mill, or a line mixer. Can be done.

[Water-repellent fiber products and their manufacturing methods]
The water-repellent fiber product of the present invention is obtained by treating a fiber material with the above-mentioned water-repellent composition. As described above, it has excellent water repellency.

The fiber material may be either a natural fiber or a chemical fiber. Examples of natural fibers include plant fibers such as cotton, cannabis, flax, palm and rush; animal fibers such as wool, goat hair, mohair, cashmere, camel and silk; and mineral fibers such as asbestos. Examples of chemical fibers include inorganic fibers such as rock fiber, metal fiber, graphite, silica, and titanate; regenerated cellulose fibers such as rayon, cupra, viscose, polynosic, and purified cellulose fibers; melt-spun cellulose fibers; Protein-based fibers such as milk protein and soybean protein; regenerated / semi-synthetic fibers such as recycled silk and alginate fibers; polyamide fibers, polyester fibers, cationic dyeable polyester fibers, polyvinyl fibers, polyacrylic alcohol fibers, polyurethane fibers, acrylic fibers, Examples thereof include synthetic fibers such as polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. Further, two or more kinds of these fibers may be composited (blended, mixed fiber, mixed weaving, mixed knitting, etc.).

Examples of the form of the fiber material include woven fabrics, knitted fabrics, fabrics, filaments, and non-woven fabrics. Examples of the use of the fiber material include objects for which antibacterial properties, water absorption, and washing resistance are imparted, such as underwear, sports clothing, bedding, and covers.

In the water-repellent fiber product of the present invention, it is preferable to treat the weaving, knitting, and dyed fiber material with the water-repellent composition. When dyeing is performed after treating the fiber material with the water repellent composition, the water repellent composition falls off from the fiber material, which is not preferable.

The amount of the urethane compound applied is preferably 0.3 to 10% by weight, more preferably 0.5 to 5% by weight, still more preferably 1 to 3% by weight, based on the fiber material. If the applied amount is less than 0.3% by weight, water repellency may not be fully developed. If the applied amount exceeds 10% by weight, it may cause a decrease in the texture and fastness of the fiber material.

The method for producing a water-repellent fiber product of the present invention includes a step of treating a fiber material with a treatment liquid containing the above-mentioned water-repellent composition.

Examples of the step include a method of treating a fiber material by a dipping method, an impregnation method, a pad drying method, a spray method or a coating method using a treatment liquid containing the above water repellent composition. Of these, the pad dry method is the most suitable in terms of productivity and economy. A known method can be adopted as the dipping method, the impregnation method, the pad drying method, the spraying method or the coating method.

As the treatment liquid, the water repellent composition of the present invention in which the above urethane compound is emulsified and dispersed in an oil-in-water mold may be used as it is, or a liquid diluted with water or the like may be used. At this time, if necessary, an antioxidant, an ultraviolet absorber, an antifoaming agent, a preservative, a fungicide, a pH adjuster, a chelating agent, a cross-linking agent and the like may be used in combination.
The weight ratio of the urethane compound to the treatment liquid is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, still more preferably 0.8 to 5% by weight.

Hereinafter, examples of the present invention will be shown and the present invention will be described in more detail, but the present invention is not limited to these examples. In addition, "part" and "%" in an example represent "part by weight" and "% by weight", respectively.

(Example 1)
In a four-necked flask equipped with a stirrer, a thermometer and a perfusion tube, sorbitandisocyanate as a polyol (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule in 500 parts by weight of methyl ethyl ketone. 400 parts by weight, hexamethylene diisocyanate (HDI) as the polyisocyanate compound (A) by 72 parts by weight, and dimethylol propanoic acid as the active hydrogen group-containing compound (B2) having a carboxyl group by 2 parts by weight, and 90 to 100 ° C. The reaction was carried out in the above for 60 minutes, and then methyl ethyl ketone (MEK) was removed from the solvent to obtain a urethane compound (X-1).

Next, 100 parts by weight of the urethane compound (X-1) obtained in the pressure-resistant autoclave, 10 parts by weight of polyoxyethylene (10 mol added) alkyl ether, 5 parts by weight of 13.6% by weight of ammonia water, and water were added. 385 parts by weight was added, and the mixture was sufficiently stirred and dispersed at 100 to 110 ° C. for 60 minutes to obtain an aqueous dispersion (Y-1). The particle size of the obtained aqueous dispersion (Y-1) was 0.98 μm in median value. The particle size was measured by diluting 1 g of the aqueous dispersion (Y-1) with 100 g of ion-exchanged water and using a laser diffraction type particle size distribution measuring device (HORIBA LA-920).

Immediately after preparing the obtained aqueous dispersion, the sample was processed under the following conditions to prepare a water-repellent sample. When the water repellency of the water-repellent sample was evaluated, it was grade 5.
Further, the aqueous dispersion (Y-1) was left to stand in an environment of 40 ° C. for 1 month and then processed into a sample in the same manner as described above to prepare a water-repellent processed sample. When the water repellency of the water-repellent sample was evaluated, it was grade 5.
These results are shown in Table 1.

<Processing conditions>
Sample cloth: Polyester tropical padding: Immersed twice, squeezed twice, drawing ratio 100% by weight
Treatment liquid: Water dispersion (Y-1) 5% by weight soln. (Amount of urethane compound in treatment liquid: 1% by weight)
Heat treatment (drying) conditions: 110 ° C x 3 minutes, 160 ° C x 1 minute

<Evaluation of water repellency>
The shower water temperature was evaluated as 25 ° C. according to the spray method of JISL1092 (1998). As a criterion, if it was grade 4 or higher, it was evaluated as having sufficient water repellency.

(Examples 2-33, Comparative Examples 1-9)
In Examples 2-33 and Comparative Examples 1-9, the polyurethane reaction composition of Example 1 was changed to that shown in Tables 1 to 4, and the amount of urethane compound in the treatment liquid was changed to% by weight shown in Tables 1 to 4. The evaluation was carried out in the same manner as in Example 1. The results are shown in Tables 1 to 4. However, Examples 30 and 31 are Reference Examples 30 and 31, respectively.

As shown in Tables 1 to 4, it can be seen that the water repellent composition of the present invention is excellent in water repellency when attached to a fiber material, and can suppress a decrease in water repellency due to diurnal change. On the other hand, in the comparative example, it can be seen that the decrease in water repellency due to diurnal change cannot be suppressed or the water repellency is low.

Claims (6)

It contains a urethane compound having a structural unit (a) derived from the organic polyisocyanate compound (A) and a structural unit (b) derived from the active hydrogen group-containing compound (B).
The structural unit (b) is a structural unit (b1) derived from a polyol (B1) having at least one hydrocarbon group having 12 or more carbon atoms in the molecule, and an active hydrogen group-containing compound (B2) having a carboxyl group. Consists of only the derived structural unit (b2)
The urethane compound is emulsified or dispersed in water.
The urethane compound has a particle size of 0.1 to 6 μm and has a particle size of 0.1 to 6 μm.
The ratio of the structural unit (b1) to the entire structural unit (b) is 60 to 99.9 mol%, and the ratio of the structural unit (b2) is 0.1 to 40 mol%.
Water repellent composition. The water repellent composition according to claim 1, wherein the molar ratio (a: b) of the structural unit (a) to the structural unit (b) is 1: 8 to 2: 1. The water repellent according to claim 1 or 2 , wherein the polyol (B1) is a compound having 2 to 5 active hydrogen groups in the molecule and 1 to 5 hydrocarbon groups having 12 or more carbon atoms. Composition. The water repellency according to any one of claims 1 to 3 , wherein the active hydrogen group-containing compound (B2) is at least one selected from 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid. Agent composition. A water-repellent fiber product obtained by treating a fiber material with the water-repellent composition according to any one of claims 1 to 4. A method for producing a water-repellent fiber product, which comprises a step of treating a fiber material with a treatment liquid containing the water-repellent composition according to any one of claims 1 to 4.