Water-repellent agent composition, water-repellent textile product and method for producing water-repellent textile product

Abstract

To provide a water-repellent agent composition that yields a water-repellent textile product with superior flexibility, a water-repellent textile product with superior flexibility, and a method for producing a water-repellent textile product.SOLUTION: A water-repellent agent composition includes a polymer (U) having constitutional units derived from the following component (A), component (B), component (C1) and component (C2). Component (A): an organic polyisocyanate compound, component (B): an organic amine compound having an active hydrogen group, component (C1): a polyol having a hydrocarbon group with 11 or more carbon atoms (excluding the component (B)), and component (C2): a polyol other than the component (C1) (excluding the component (B)).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a water repellent composition capable of imparting excellent flexibility, a water repellent textile product using said water repellent composition, and a method for producing the water repellent textile product. [Background technology]

[0002] Traditionally, textile products coated with fluorine-based water repellents having fluorine-containing groups have been widely used because of their high water repellency. However, there are concerns about the accumulation of fluorine-based compounds in the human body, and there has been much development of water repellent materials using non-fluorine-based compounds.

[0003] Conventionally, paraffin wax, silicone resin, etc. are well known as water repellent compositions that do not contain fluorine-based compounds, but their water repellency is inferior to that of fluorine-based compounds. In recent years, a technique using a composition that does not contain fluorine-based compounds has been proposed in which water repellency is obtained by treating a composition containing an agent that provides a surface effect and a polymer extender composition. Here, the polymer extender composition is a urethane compound having an alkyl group, and this composition alone can provide a certain degree of water repellency (Patent Document 1). In addition, Patent Document 2 proposes that a composition containing an organic urethane compound has durable water repellency. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2016-522330 [Patent Document 2] Special Publication No. 2016-524628 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although these conventional water repellent compositions can impart water repellency, the flexibility of the treated textile product may be reduced. When the flexibility of a textile product is reduced, there is concern that the usability and processability may be reduced, limiting the applicable uses. On the other hand, there is a method of using a softener in combination with the conventional water repellent composition to prevent the flexibility of the composition from being reduced, but the use of the softener may result in a reduction in water repellency. Therefore, there has been a demand for a water repellent composition that can impart excellent flexibility. An object of the present invention is to provide a water repellent composition which can provide a water repellent textile product having excellent flexibility, a water repellent textile product having excellent flexibility, and a method for producing the water repellent textile product. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors conducted extensive research to find that the above problems could be solved by a water repellent composition containing a specific polymer, and thus arrived at the present invention. That is, the present invention includes the following aspects. <1> A water repellent composition comprising a polymer (U) having structural units derived from the following components (A), (B), (C1) and (C2): Component (A): Organic polyisocyanate compound Component (B): Organic amine compound having an active hydrogen group Component (C1): Polyol having a hydrocarbon group having 11 or more carbon atoms (excluding the above-mentioned component (B)) Component (C2): A polyol other than the component (C1) (but excluding the component (B)) <2> The component (B) contains an organic amine compound having at least one group selected from a secondary amino group, a tertiary amino group, and a hydroxyl group. <1> The water repellent composition according to claim 1. <3> The component (B) contains an organic amine compound having a tertiary amino group. <1> or <2> The water repellent composition according to claim 1. <4> The component (C2) contains a polyol having three or more active hydrogen groups. <1> ~ <3> 13. The water repellent composition according to claim 12, <5> The component (C1) contains a polyol having two or more hydrocarbon groups each having 11 or more carbon atoms. <1> ~ <4> 13. The water repellent composition according to claim 12, <6> the molar ratio (a / b) of the structural unit (a) derived from the component (A) to the structural unit (b) derived from the component (B) is 2 to 20; <1> ~ <5> 13. The water repellent composition according to claim 12, <7> the molar ratio (a / c1) of the structural unit (a) derived from the component (A) to the structural unit (c1) derived from the component (C1) is 0.8 to 5; <1> ~ <6> 13. The water repellent composition according to claim 12, <8> For textile materials, <1> ~ <7> 2. A water-repellent textile product treated with the water repellent composition according to claim 1. <9> The fiber material, <1> ~ <7> 2. A method for producing a water-repellent textile product, comprising a step of treating the textile product with a treatment liquid containing the water repellent composition according to any one of claims 1 to 11. Effect of the Invention

[0007] The water-repellent textile products to which the water-repellent composition of the present invention is applied have excellent flexibility. The water-repellent textile product of the present invention has excellent softness. According to the method for producing a water-repellent textile product of the present invention, a water-repellent textile product having excellent flexibility can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention relates to a water repellent composition containing a specific polymer.

[0009] Polymer The water repellent composition of the present invention contains a polymer (U) having structural units derived from the following components (A), (B), (C1) and (C2). Component (A): Organic polyisocyanate compound Component (B): Organic amine compound having an active hydrogen group Component (C1): Polyol having a hydrocarbon group having 11 or more carbon atoms (excluding the above-mentioned component (B)) Component (C2): A polyol other than the component (C1) (but excluding the component (B)) The polymer (U) may be used alone or in combination of two or more kinds.

[0010] (Component (A)) Component (A) is an organic polyisocyanate. Component (A) is a constituent of polymer (U) 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. Component (A) may be used alone or in combination with two or more kinds. Here, the constituent unit (a) derived from component (A) refers to a unit constituted using component (A) as a raw material, and includes the structure of "-NHC(=O)-" among urethane bonds.

[0011] Examples of the component (A) include aromatic polyisocyanates (A1) having 8 to 26 carbon atoms, aliphatic polyisocyanates (A2) having 4 to 22 carbon atoms, alicyclic polyisocyanates (A3) having 8 to 18 carbon atoms, araliphatic polyisocyanates (A4) having 10 to 18 carbon atoms, and modified products (A5) of these polyisocyanates (A1) to (A4).

[0012] Examples of the aromatic polyisocyanate (A1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate will be abbreviated as TDI), crude TDI, 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate will be abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and m- or p-isocyanatophenylsulfonyl isocyanate.

[0013] Examples of the aliphatic polyisocyanate (A2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 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.

[0014] 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, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0015] Examples of the aralkyl polyisocyanate (A4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

[0016] The modified polyisocyanates (A1) to (A4) (A5) include modified polyisocyanates (A1) to (A4) containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group in the molecule. The modified polyisocyanates (A1) to (A4) (A5) include, for example, 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.

[0017] Among these components (A), from the viewpoint of water repellency, it is preferable to include at least one selected from the aromatic polyisocyanate (A1) having 8 to 26 carbon atoms and the aliphatic polyisocyanate (A2) having 4 to 22 carbon atoms, and it is more preferable to include the aliphatic polyisocyanate (A2) having 4 to 22 carbon atoms. More specifically, it is particularly preferable that the resin contains at least one selected from tetramethylene diisocyanate, HDI, and octamethylene diisocyanate, and it is most preferable that the resin contains HDI.

[0018] (Component (B)) Component (B) is an organic amine compound having an active hydrogen group. Component (B) is a constituent of polymer (U) and is not particularly limited as long as it is an organic amine compound having an active hydrogen group. 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 constituent unit (b) derived from component (B) refers to a unit formed using an organic amine compound having an active hydrogen group as a raw material, and refers to the remainder obtained by removing active hydrogen (active hydrogen that contributes to the reaction with component (A)) from an organic amine compound having an active hydrogen group. From the viewpoint of flexibility, component (B) preferably contains an organic amine compound having at least one selected from a secondary amino group, a tertiary amino group, and a hydroxyl group, more preferably contains an organic amine compound having a tertiary amino group, further preferably contains an organic amine compound having a tertiary amino group and at least one selected from a primary amino group, a secondary amino group, and a hydroxyl group, and particularly preferably contains an organic amine compound having a tertiary amino group and a hydroxyl group. Only one type of component (B) may be used, or two or more types may be used.

[0019] Examples of the component (B) include an organic amine compound (B1) having no tertiary amino group but an active hydrogen group, and an organic amine compound (B2) having a tertiary amino group and an active hydrogen group.

[0020] Examples of the organic amine compound (B1) having no tertiary amino group but an active hydrogen group include monoethanolamine, diethanolamine, diethylenetriamine, dibutylamine, ethylenediamine, tetraethylenediamine, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylamine, N-methylamino ... Examples of the hydrazine include hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazidopropionic acid hydrazide, and 3-semicarbazidopropylcarbazate. Examples of the organic amine compound (B2) having a tertiary amino group and an active hydrogen group include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dibutylaminopropylamine.

[0021] From the viewpoint of flexibility, these components (B) preferably contain an organic amine compound (B2) having a tertiary amino group and an active hydrogen group, and more preferably contain at least one selected from N-methyldiethanolamine, N,N-dimethylethanolamine, and N,N-dimethylaminopropylamine.

[0022] (component C1) Component (C1) is a polyol having a hydrocarbon group with 11 or more carbon atoms, excluding the organic amine compound having an active hydrogen group, which is component (B). Only one type of component (C1) may be used, or two or more types may be used. The structural unit (c1) derived from component (C1) refers to the remainder obtained by removing active hydrogen (active hydrogen that contributes to the reaction with organic polyisocyanate compound (A)) from component (C1). From the viewpoint of water repellency, component (C1) preferably contains a polyol having 2 or more hydrocarbon groups in the molecule. The upper limit of the number of hydrocarbon groups is more preferably 5, and even more preferably 3. Also, for example, 2 to 5 is more preferable, and 2 to 3 is even more preferable. From the viewpoint of water repellency, component (C1) preferably contains a polyol having 2 to 4 hydroxyl groups in the molecule, and more preferably contains a polyol having 2 to 3 hydroxyl groups. The hydrocarbon group of component (C1) may have a straight-chain or branched structure, and may be saturated or unsaturated. From the viewpoint of water repellency, it is preferable for the component (C1) to include a polyol having a hydrocarbon group with a straight-chain structure, and it is even more preferable for the component (C1) to include a polyol having a hydrocarbon group with a straight-chain saturated structure. From the viewpoint of water repellency, component (C1) preferably contains a polyol having a hydrocarbon group having 11 to 29 carbon atoms. The upper limit of the carbon number is preferably 27, more preferably 23, and even more preferably 21. On the other hand, the lower limit of the carbon number is more preferably 13, and particularly preferably 17. Also, for example, 13 to 23 is more preferable, and 17 to 21 is even more preferable.

[0023] There are no particular limitations on component (C1) so long as it is a polyol having a hydrocarbon group having 11 or more carbon atoms. From the viewpoint of water repellency, however, it is preferable for the component (C1-1) to contain a polyol having an ester bond between a fatty acid having 12 or more carbon atoms and a polyhydric alcohol having a valence of 3 or more (hereinafter, sometimes simply referred to as polyol (C1-1)). The fatty acid having 12 or more carbon atoms may have a straight-chain or branched structure, and may be saturated or unsaturated. The number of carbon atoms in the hydrocarbon group of the fatty acid having 12 or more carbon atoms is preferably 11 to 29 in terms of water repellency. The upper limit of the carbon number is more preferably 25, and even more preferably 21. On the other hand, the lower limit of the carbon number is more preferably 13, and even more preferably 17. Furthermore, for example, 13 to 25 is more preferable, and 17 to 21 is more preferable.

[0024] Examples of fatty acids having 12 or more carbon atoms include lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoeicosaic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosanoic acid, nervonic acid, cerotic acid, montanic acid, melissic acid, etc. Among these, myristic acid, palmitic acid, stearic acid, isostearic acid, and behenic acid are preferred from the viewpoint of water repellency, and stearic acid and behenic acid are more preferred.

[0025] Examples of trihydric or higher polyhydric alcohols include glycerin, sorbitan, sorbitol, pentaerythritol, erythritol, alditols other than those mentioned above, trimethylolpropane, diglycerin, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, sucrose, castor oil, hydrogenated castor oil, and alkylene oxide adducts thereof, etc. Among these, glycerin, sorbitol, pentaerythritol, and erythritol are preferred from the viewpoint of water repellency, and sorbitol and pentaerythritol are more preferred.

[0026] The number of ester bonds in the polyol (C1-1) is, from the viewpoint of water repellency, 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 the polyol (C1-1) having an ester bond between a fatty acid having 12 or more carbon atoms and a polyhydric alcohol having a valence of 3 or more is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3.

[0027] From the viewpoint of water repellency, the polyol (C1-1) preferably includes at least one selected from ditrimethylolpropane distearate, ditrimethylolpropane monostearate, ditrimethylolpropane dibehenate, ditrimethylolpropane monobehenate, sorbitan distearate, sorbitan monostearate, sorbitan dibehenate, sorbitan monobehenate, distearyl erythritol, monostearyl erythritol, dibehenyl erythritol, monobehenyl erythritol, distearyl pentaerythritol, monostearyl pentaerythritol, dibehenyl pentaerythritol, and monobehenyl pentaerythritol. More preferably, the copolymer contains at least one selected from the group consisting of sorbitan distearate, distearyl erythritol, distearyl pentaerythritol, monostearyl pentaerythritol, sorbitan dibehenate, sorbitan monobehenate, dibehenyl erythritol, monobehenyl erythritol, dibehenyl pentaerythritol, and monobehenyl pentaerythritol; further preferably, the copolymer contains at least one selected from the group consisting of sorbitan distearate, distearyl erythritol, distearyl pentaerythritol, sorbitan dibehenate, dibehenyl erythritol, and dibehenyl pentaerythritol; and particularly preferably, the copolymer contains at least one selected from the group consisting of sorbitan distearate, distearyl pentaerythritol, sorbitan dibehenate, and dibehenyl pentaerythritol. The method for producing the polyol (C1-1) is not particularly limited, and any known method can be used.

[0028] (component C2) Component (C2) is a polyol other than component (C1), excluding the organic amine compound having an active hydrogen group, which is component (B). Component (C2) may be used alone or in combination with two or more kinds. The structural unit (c2) derived from component (C2) refers to the remainder obtained by removing active hydrogen (active hydrogen that contributes to the reaction with organic polyisocyanate compound (A)) from component (C2). From the viewpoint of water repellency, the component (C2) preferably contains a polyol having 2 to 6 hydroxyl groups in the molecule, more preferably 2 to 5 hydroxyl groups, and even more preferably 2 to 4 hydroxyl groups.

[0029] The molecular weight of component (C2) is not particularly limited, but from the viewpoint of water repellency, it is preferable that the component (C2) contains a polyol having a molecular weight of 3,000 or less. The upper limit of the molecular weight is more preferably 2,000 or less, and even more preferably 1,000 or less. On the other hand, the lower limit of the molecular weight is preferably 90. Also, for example, the molecular weight is preferably 90 to 2,000, and more preferably 90 to 1,000. From the viewpoint of water repellency, the component (C2) preferably contains at least one selected from a diol component and a tri- or higher functional polyol, and more preferably contains a tri- or higher functional polyol. Specific examples of the component (C2) include diol components (molecular weight 3,000 or less) such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 3,000 or less), propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (molecular weight 3,000 or less), butylene glycol, dibutylene glycol, tributylene glycol, polybutylene glycol (molecular weight 3,000 or less), 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, tetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, resorcin, hydroquinone, bisphenol A or its alkylene oxide adduct; and trifunctional or higher polyols such as trimethylolethane, trimethylolpropane, glycerin, sorbitol, pentaerythritol, and ditrimethylolpropane. Among these components (C2), from the viewpoint of water repellency, it is preferable to include at least one selected from trimethylolethane, trimethylolpropane, glycerin, sorbitol, pentaerythritol, and ditrimethylolpropane, and it is more preferable to include at least one selected from glycerin, sorbitol, pentaerythritol, and ditrimethylolpropane.

[0030] (Other active hydrogen group-containing compounds (D)) The polymer (U) may contain a structural unit derived from another active hydrogen group-containing compound (D), which is an active hydrogen group-containing compound other than the components (B), (C1) and (C2), as long as the effect of the present invention is not impaired.

[0031] Other examples of the active hydrogen group-containing compound (D) include monool components such as methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol, nonanol, phenol, and benzyl alcohol, and polyhydric alcohol esters having one hydroxyl group such as ditrimethylolpropane tristearate and ditrimethylolpropane tribehenate.

[0032] (Polymer (U)) In the polymer (U), the molar ratio (a / b) of the structural unit (a) derived from component (A) to the structural unit (b) derived from component (B) is preferably from the viewpoint of flexibility to be 2 to 20. The upper limit of the molar ratio is more preferably 18, further preferably 15, and particularly preferably 13. On the other hand, the lower limit of the molar ratio is more preferably 2.5, further preferably 3, and particularly preferably 3.5. Also, for example, 2.5 to 18 is more preferable, 3 to 15 is more preferable, and 3.5 to 13 is particularly preferable. The molar ratio of the structural unit (a) to the structural unit (b) is derived from the molar ratio of the component (A) to the component (B) when producing the polymer (U).

[0033] In the polymer (U), the molar ratio (a / c1) of the structural unit (a) derived from component (A) to the structural unit (c1) derived from component (C1) is preferably 0.8 to 5 in terms of water repellency. The upper limit of the molar ratio is more preferably 4, further preferably 3, and particularly preferably 2. On the other hand, the lower limit of the molar ratio is more preferably 0.85, further preferably 0.9, and particularly preferably 1. Also, for example, it is more preferably 0.85 to 4, further preferably 0.9 to 3, and particularly preferably 1 to 2. The molar ratio of the structural unit (a) to the structural unit (c1) is derived from the molar ratio of the component (A) to the component (C1) when producing the polymer (U).

[0034] The weight average molecular weight of the polymer (U) is preferably 4,000 to 2,000,000 in terms of water repellency. The upper limit of the average molecular weight is more preferably 1,750,000, further preferably 1,500,000, and particularly preferably 1,000,000. On the other hand, the lower limit of the average molecular weight is more preferably 6,000, further preferably 8,000, and particularly preferably 10,000. Also, for example, it is more preferably 6,000 to 1,750,000, further preferably 8,000 to 1,500,000, and particularly preferably 10,000 to 1,000,000.

[0035] From the viewpoint of water repellency, the degree of polymerization of the polymer (U) is preferably 4 to 2,000. The upper limit of the degree of polymerization is more preferably 1,500, further preferably 1,000, and particularly preferably 700. On the other hand, the lower limit of the degree of polymerization is more preferably 4, further preferably 6, and particularly preferably 8. Also, for example, it is more preferably 4 to 1,500, further preferably 6 to 1,000, and particularly preferably 8 to 700.

[0036] The hydroxyl value of the polymer (U) is preferably 0 to 100 mgKOH / g in terms of water repellency. The upper limit of the hydroxyl value is more preferably 90 mgKOH / g, even more preferably 85 mgKOH / g, and particularly preferably 80 mgKOH / g. On the other hand, the lower limit of the hydroxyl value is more preferably 1 mgKOH / g, even more preferably 3 mgKOH / g, and particularly preferably 5 mgKOH / g. Also, for example, it is more preferably 1 to 90 mgKOH / g, even more preferably 3 to 85 mgKOH / g, and particularly preferably 5 to 80 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K 1557-1:2007.

[0037] The method for producing the polymer (U) is not particularly limited as long as it is a urethane reaction method, but the polymer (U) can be obtained by reacting the components (A), (B), (C1), and (C2), and other active hydrogen group-containing compounds (D) as optional components, and a known method for producing urethane can be adopted. For example, the method may be a one-shot method in which all components are reacted at the same time, a multi-stage method in which an active hydrogen group-containing compound is gradually added to a polyisocyanate compound and reacted, or a prepolymer method in which an active hydrogen group-containing compound is reacted with a polyisocyanate compound to synthesize a prepolymer having an isocyanate at the end, and then a chain extender is reacted therewith.

[0038] Examples of the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic acid dihydrazide, adipic acid dihydrazide, glutaraldehyde, ethylhexylamine, butylaminoethyl ... Chain extenders having an amino group such as acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazidopropionic acid hydrazide, and 3-semicarbazidopropylcarbazate; and chain extenders having a hydroxyl group such as 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, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, and trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

[0039] When producing the polymer (U), 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, and N-methylmorpholine, metal salts such as potassium acetate, zinc stearate, and tin octoate, and organometallic compounds such as dibutyl laurate.

[0040] [Water repellent composition] The water repellent composition of the present invention contains the above-mentioned polymer (U). By containing the polymer (U), when the water repellent composition is attached to a textile material, a water repellent textile product having excellent flexibility can be obtained. The reason why the water repellent composition of the present invention has excellent flexibility is believed to be that the inclusion of structural units derived from components (A) and (B) gives polymer (U) a high affinity with fibers, that the inclusion of structural units derived from components (A) and (C1) allows polymer (U) to reduce fiber-to-fiber friction, and that polymer (U) containing structural units derived from components (A), (B), (C1) and (C2) can reduce entanglement of fibers. The concept of the water repellent composition of the present invention includes a composition that is composed of a component that exerts a water repellent function, such as the above-mentioned polymer (U) or a fluorine-based water repellent having a fluorine atom in the molecule (hereinafter referred to as a water repellent component), a composition that contains the water repellent component and other components, and a composition in which the water repellent component is dissolved, emulsified or dispersed in water and / or an organic solvent, etc. The water repellent composition of the present invention is preferable in that it is substantially free of a fluorine-based water repellent (non-fluorine-based water repellent composition), but is not limited thereto.

[0041] In terms of processability, the water repellent composition of the present invention is preferably prepared by dissolving, emulsifying or dispersing the polymer (U) in water and / or an organic solvent. The proportion of the polymer (U) in the non-volatile content of the water repellent composition (dissolved, dispersed or emulsified product) is preferably 10 to 100% by weight in terms of water repellency. The lower limit of the proportion is more preferably 20% by weight, even more preferably 30% by weight, and particularly preferably 50% by weight. Also, for example, it is more preferably 20 to 100% by weight, even more preferably 30 to 100% by weight, and particularly preferably 50 to 100% by weight. Here, the non-volatile content (also referred to as solid content) is the residue when 1.7 to 1.8 g of the sample is spread evenly on an aluminum sheet and dried at 110° C. under irradiation with an infrared lamp, and the measurement is terminated when the fluctuation range of the volatile content for 150 seconds becomes 0.15% by weight.

[0042] The average particle size of the components emulsified and / or dispersed in water in the water repellent composition of the present invention is preferably 0.01 to 8 μm in terms of stability as a median value (middle value). The upper limit of the average particle size is more preferably 7 μm, even more preferably 6 μm, and particularly preferably 5 μm. On the other hand, the lower limit of the average particle size is more preferably 0.03 μm, even more preferably 0.05 μm, and particularly preferably 0.10 μm. Also, for example, 0.03 to 7 μm is more preferable, 0.05 to 6 is even more preferable, and 0.10 to 5 μm is particularly preferable. In the present invention, the median value (middle value) means the median value (middle value) of particle sizes based on volume.

[0043] When the polymer (U) is dissolved, emulsified or dispersed in water and / or an organic solvent, the water repellent composition of the present invention may further use a surfactant. The proportion of the surfactant is preferably 1 to 40 parts by weight relative to 100 parts by weight of the polymer (U) in terms of water repellency and stability. The upper limit of the weight parts is more preferably 30 parts by weight, further preferably 20 parts by weight, and particularly preferably 15 parts by weight. On the other hand, the lower limit of the weight parts is more preferably 3 parts by weight, further preferably 5 parts by weight, and particularly preferably 7 parts by weight. Also, for example, 3 to 30 parts by weight is more preferably, 5 to 20 parts by weight is more preferably, and 7 to 15 parts by weight is particularly preferred.

[0044] A suitable surfactant is preferably a nonionic surfactant from the viewpoint of stability, and may further include at least one selected from a cationic surfactant and an anionic surfactant. One or more surfactants may be used in combination.

[0045] Examples of nonionic surfactants 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, and polyoxyethylene isostearyl ether; polyoxyalkylene secondary alkyl ethers such as polyoxyethylene 1-hexylhexyl ether, polyoxyethylene 1-octylhexyl ether, polyoxyethylene 1-hexyloctyl ether, polyoxyethylene 1-pentylheptyl ether, and polyoxyethylene 1-heptylpentyl ether; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene dodecylphenyl ether; polyoxyethylene Polyoxyalkylene alkylaryl phenyl ethers such as tristyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, and polyoxyethylene benzyl phenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristylate, polyoxyethylene dilaurate, polyoxyethylene diolate, polyoxyethylene dimyristylate, and polyoxyethylene distearate; sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, and glycerin monopalmitate; polyoxyalkylene sorbitol fatty acid esters;Examples of such copolymers include sucrose fatty acid esters; polyoxyalkylene castor oil ethers such as polyoxyethylene castor oil ether; polyoxyalkylene hydrogenated castor oil ethers such as polyoxyethylene hydrogenated castor oil ether; polyoxyalkylene alkylamino ethers such as polyoxyethylene lauryl amino ether and polyoxyethylene stearyl amino ether; oxyethylene-oxypropylene block or random copolymers; terminal alkyl etherified products of oxyethylene-oxypropylene block or random copolymers; terminal sucrose etherified products of oxyethylene-oxypropylene block or random copolymers; and the like.

[0046] Examples of anionic surfactants include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, and triethanolamine oleate; hydroxyl group-containing carboxylic acids (salts) such as hydroxyacetic acid, potassium hydroxyacetate, lactic acid, and potassium lactate; polyoxyalkylene alkyl ether acetic acids (salts) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); salts of carboxyl group-polysubstituted aromatic compounds such as potassium trimellitate and potassium pyromellitic acid; alkyl benzene sulfonic acids (salts) such as dodecyl benzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acids (salts) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); higher fatty acid amide sulfosulfates such as stearoyl methyl taurine (sodium), lauroyl methyl taurine (sodium), myristoyl methyl taurine (sodium), and palmitoyl methyl taurine (sodium). aromatic phosphonic acids (salts) such as phenylphosphonate (potassium salt); alkylphosphonic acid alkyl phosphate esters (salts) such as 2-ethylhexyl phosphonate mono 2-ethylhexyl ester (potassium salt); nitrogen-containing alkyl phosphonic acids (salts) such as aminoethylphosphonic acid (diethanolamine salt); alkyl sulfate esters (salts) such as 2-ethylhexyl sulfate (sodium salt); polyoxyalkylene sulfate esters (salts) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate, and long-chain N-acyl glutamates such as sodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate.

[0047] Examples of cationic surfactants include alkyl quaternary ammonium salts such as lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl ammonium chloride, beef tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, coconut oil alkyl trimethyl ammonium bromide, cetyl trimethyl ammonium methosulfate, oleyl dimethylethyl ammonium ethosulfate, dioctyl dimethyl ammonium chloride, dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and octadecyl diethyl methyl ammonium sulfate; (polyoxyethylene) lauryl amino ether lactate, stearyl amino ether lactate, and di(polyoxyethylene) lauryl methyl amino ether lactate. (Polyoxyalkylene) alkylamino ether salts such as ether dimethyl phosphate, di(polyoxyethylene) lauryl ethyl ammonium ethosulfate, di(polyoxyethylene) hardened beef tallow alkyl ethyl amine ethosulfate, di(polyoxyethylene) lauryl methyl ammonium dimethyl phosphate, and di(polyoxyethylene) stearyl amine lactate; acyl amido alkyl quaternary ammonium salts such as N-(2-hydroxyethyl)-N,N-dimethyl-N-stearoyl amido propyl ammonium nitrate, lanolin fatty acid amido propyl ethyl dimethyl ammonium ethosulfate, and lauroyl amido ethyl methyl diethyl ammonium methosulfate; alkyl ethenoxy quaternary ammonium salts such as dipalmityl polyethenoxy ethyl ammonium chloride and distearyl polyethenoxy methyl ammonium chloride; alkyl isoquinolinium salts such as lauryl isoquinolinium chloride; benzalkonium salts such as lauryl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride;Benzethonium salts such as benzyldimethyl{2-[2-(p-1,1,3,3-tetramethylbutylphenoxy)ethoxy]ethyl}ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts such as oleyl hydroxyethyl imidazolinium ethosulfate and lauryl hydroxyethyl imidazolinium ethosulfate; acyl basic amino acid alkyl ester salts such as N-cocoyl arginine ethyl ester pyrrolidone carboxylate and N-lauroyl lysine ethyl ester chloride; primary amine salts such as laurylamine chloride, stearylamine bromide, hardened beef tallow alkylamine chloride, and rosinamine acetate; cetylmethylamine sal secondary amine salts such as dilauryl methylamine sulfate, lauryl diethylamine chloride, lauryl ethylamine bromide, lauryl propylamine acetate, dioctylamine chloride, and octadecylethylamine hydroxide; tertiary amine salts such as dilauryl methylamine sulfate, lauryl diethylamine chloride, lauryl ethyl methylamine bromide, diethanol stearyl amidoethylamine trihydroxyethyl phosphate salt, and stearyl amidoethylethanolamine urea polycondensate acetate salt; fatty acid amide guanidinium salts; and alkyl trialkylene glycol ammonium salts such as lauryl triethylene glycol ammonium hydroxide.

[0048] The water may be any of pure water, distilled water, purified water, soft water, ion-exchanged water, tap water, and the like. Examples of the organic solvent that can be used 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, amide solvents such as dimethylformamide and N-methylpyrrolidone, aromatic solvents such as toluene and xylene, etc. These organic solvents may be used alone or in combination of two or more kinds.

[0049] The water repellent composition of the present invention may contain other components in addition to the polymer (U), surfactant, water and organic solvent, within the scope of not impairing the effects of the present invention. Examples of other components include discoloration inhibitors, antibacterial agents, antifungal agents, insect repellents, anti-dust mites, deodorants, antistatic agents, water and oil repellents, UV absorbers, flame retardants, stain repellents, deep color agents, smoothing agents, softeners, water absorbents and other fiber post-processing agents, oils, surfactants, inorganic substances, preservatives, pH adjusters, defoamers, solvents, fatty acids (salts), etc.

[0050] The method for producing the water repellent composition of the present invention is not particularly limited, and a known method can be used. For example, the water repellent composition can be obtained by mixing the polymer (U) obtained by the above method, a surfactant, water and an organic solvent, and emulsifying the mixture using a general stirring device and an emulsifying device such as a homomixer, a homogenizer, a colloid mill, or a line mixer.

[0051] [Water-repellent textile products and their manufacturing method] The water-repellent textile product of the present invention is produced by treating a textile material with the above-mentioned water repellent composition.

[0052] The fiber material may be either natural or chemical. Examples of natural fibers include plant fibers such as cotton, hemp, 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 refined cellulose fibers; melt-spun cellulose fibers; protein fibers such as milk protein and soy protein; regenerated and semi-synthetic fibers such as regenerated silk and alginic acid fibers; and synthetic fibers such as polyamide fibers, polyester fibers, cationic dyeable polyester fibers, polyvinyl fibers, polyacryl alcohol fibers, polyurethane fibers, acrylic fibers, polyethylene fibers, polyvinylidene fibers, and polystyrene fibers. In addition, two or more of these fibers may be composited (mixed spinning, mixed fibers, interwoven, interknitted, etc.).

[0053] Examples of the form of the fiber material include woven fabric, knitted fabric, cloth, thread, nonwoven fabric, etc. Examples of applications of the fiber material include objects to which antibacterial properties, water absorbency, and washability are to be imparted, such as underwear, sportswear, bedding, covers, etc.

[0054] The water-repellent textile product of the present invention is preferably prepared by treating a textile material that has been woven, knitted or dyed with the water repellent composition. If the textile material is treated with the water repellent composition and then dyed, this is not preferred because the water repellent composition falls off from the textile material.

[0055] The amount of polymer (U) attached to the fiber material is preferably 0.1 to 10% by weight from the viewpoint of water repellency. The upper limit of the amount attached is more preferably 7% by weight, further preferably 5% by weight, and particularly preferably 3% by weight. On the other hand, the lower limit of the amount attached is more preferably 0.2% by weight, further preferably 0.25% by weight, and particularly preferably 0.3% by weight. Also, for example, it is more preferably 0.2 to 7% by weight, further preferably 0.25 to 5% by weight, and particularly preferably 0.3 to 5% by weight.

[0056] The method for producing a water-repellent textile product of the present invention comprises the step of treating a textile material with a treatment liquid containing the above-mentioned water repellent composition.

[0057] The step includes a method of treating a fiber material with a treatment liquid containing the water repellent composition by a dipping method, an impregnation method, a pad-drying method, a spraying method, or a coating method. Among these, the pad-drying method is most suitable in terms of productivity and economy. As the dipping method, the impregnation method, the pad-drying method, the spraying method, or the coating method, a known method can be used.

[0058] The water repellent composition of the present invention may be used as it is as the treatment liquid, or may be diluted with water or an organic solvent. In this case, an antioxidant, an ultraviolet absorber, an antifoaming agent, an antiseptic, an antifungal agent, a pH adjuster, a chelating agent, a crosslinking agent, etc. may be used in combination, if necessary. The proportion of the polymer (U) in the treatment liquid is preferably 0.1 to 10% by weight from the viewpoint of water repellency and flexibility. The upper limit of the proportion is more preferably 8% by weight, further preferably 5% by weight, and particularly preferably 3% by weight. On the other hand, the lower limit of the proportion is more preferably 0.3% by weight, further preferably 0.5% by weight, and particularly preferably 0.7% by weight. EXAMPLES

[0059] The present invention will be described in more detail below by showing examples of the present invention, but the present invention is not limited to these examples.

[0060] Example 1 A four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 300 parts by weight of methyl ethyl ketone (MEK), 0.2 mol of N-methyldiethanolamine as an organic amine compound having an active hydrogen group (component (B)), 1 mol of hexamethylene diisocyanate (HDI) as a polyisocyanate compound (component (A)), 0.7 mol of sorbitan distearate as a polyol having a hydrocarbon group with 11 or more carbon atoms (component (C1)), 0.05 mol of 1,6-hexanediol as a polyol component other than C1 (component (C2)), and 0.05 mol of glycerin, and reacted for 60 minutes at 90 to 100°C under a nitrogen atmosphere, and then the MEK was removed to obtain a reaction product, polymer (U) (X-1).

[0061] Next, 100 parts by weight of the obtained polymer (U) (X-1), 10 parts by weight of polyoxyethylene (10 mole addition) stearyl ether, 5 parts by weight of acetic acid, and 385 parts by weight of water were added to a pressure-resistant autoclave, and the mixture was thoroughly stirred and dispersed at 100 to 110°C for 60 minutes to obtain a water dispersion, a water repellent composition (Y-1).

[0062] Immediately after preparation of the water repellent composition, the resulting water repellent composition was processed into a sample under the following conditions to prepare a water repellent sample. The water repellency of the water repellent sample was evaluated as grade 5. The water repellent sample was also washed 20 times under the following conditions, and the water repellency was evaluated as grade 3. The flexibility of the water-repellent sample was evaluated under the following conditions and given a grade of 4. The results are shown in Table 1.

[0063] <Processing conditions> Sample fabric: Polyester tropical Padding: 2x dipping, 2x squeezing, squeezing rate 100% by weight Treatment liquid: Water dispersion (Y-1) 5% by weight soln. (Amount of polymer (U) in the treatment liquid: 1% by weight) Heat treatment (drying) conditions: 110℃ x 3 minutes, 160℃ x 1 minute

[0064] <Washing Instructions> The water-repellent sample was washed according to JIS-L-0217, Method 103. The detergent used was Attack (Kao Corporation), and the detergent concentration in the washing liquid was 1.0 g / L. Under the above conditions, the sample was repeatedly washed 20 times.

[0065] <Evaluation of water repellency> The evaluation was conducted according to the JIS-L-1092 spray method with shower water at 25°C. The evaluation criteria were grade 4 or higher, which was deemed to have sufficient water repellency. After 20 washes, the evaluation criteria were grade 2 or higher, which was deemed to have sufficient washing durability water repellency.

[0066] <Evaluation of flexibility (handling ability)> The feel of the water-repellent samples was evaluated by handling on the following 5-point scale. As a criterion, if it was better than grade 3, it had sufficient flexibility and was evaluated as good. For example, grades 3 to 4 are evaluation results between grades 3 and 4, and indicate softer than grade 3. Grade 5: Much softer than untreated fabric Grade 4: Slightly softer than untreated fabric Grade 3: Equivalent to untreated fabric Grade 2: Slightly harder than untreated fabric Grade 1: Much harder than untreated fabric

[0067] <Flexibility rating (B value)> The flexibility was evaluated using a bending tester (Kato Tech, KES-FB2) and the B value. The B value of the untreated fabric was 1.22 gf×cm 2 / cm, the smaller the value, the better the flexibility.

[0068] (Examples 2 to 11, Comparative Examples 1 to 9) Examples 2 to 11 and Comparative Examples 1 to 9 were evaluated in the same manner as in Example 1, except that the reaction compositions in Example 1 were changed to those shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0069] [Table 1]

[0070] [Table 2]

[0071] As shown in Tables 1 and 2, the water repellent compositions of the present invention described in Examples 1 to 11 were excellent in water repellency, washing durability, and softness when applied to a textile material. On the other hand, when component (B) was not used (Comparative Examples 1 to 3), the softness was poor and the problem of the present application could not be solved, and when component (C1) was not used (Comparative Example 4), when component (C2) was not used (Comparative Example 5), and when a polyol having a hydrocarbon group with 4 to 10 carbon atoms was used instead of component (C1) (Comparative Examples 6 to 8), the water repellency was poor and the compositions were not suitable as water repellents.

Claims

1. A water repellent composition comprising a polymer (U) having structural units derived from the following components (A), (B), (C1) and (C2): Component (A): Organic polyisocyanate compound Component (B): Organic amine compound having an active hydrogen group Component (C1): Polyol having a hydrocarbon group having 11 or more carbon atoms (excluding the above-mentioned component (B)) Component (C2): A polyol other than the component (C1) (but excluding the component (B))

2. 2. The water repellent composition according to claim 1, wherein the component (B) comprises an organic amine compound having at least one group selected from a secondary amino group, a tertiary amino group, and a hydroxyl group.

3. The water repellent composition according to claim 1 or 2, wherein the component (B) comprises an organic amine compound having a tertiary amino group.

4. The water repellent composition according to claim 1 or 2, wherein the component (C2) comprises a polyol having three or more active hydrogen groups.

5. 3. The water repellent composition according to claim 1, wherein the component (C1) comprises a polyol having two or more hydrocarbon groups each having 11 or more carbon atoms.

6. 3. The water repellent composition according to claim 1, wherein a molar ratio (a / b) of the structural unit (a) derived from the component (A) to the structural unit (b) derived from the component (B) is 2 to 20.

7. The water repellent composition according to claim 1 or 2, wherein the molar ratio (a / c1) of the structural unit (a) derived from the component (A) to the structural unit (c1) derived from the component (C1) is 0.8 to 5.

8. A water-repellent textile product obtained by treating a textile material with the water repellent composition according to claim 1 or 2.

9. A method for producing a water-repellent textile product, comprising a step of treating a textile material with a treatment liquid containing the water repellent composition according to claim 1 or 2.

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