Method for producing liquid-repellent fibers

Abstract

The present disclosure addresses the problem of providing a method for imparting liquid repellency to fibers even when the amount of water and/or a surfactant is reduced, preferably without using water and/or a surfactant. Provided is a method for producing liquid-repellent fibers, the method comprising a fiber treatment step in which supercritical carbon dioxide is used as a treatment medium and a fiber base material is treated with a repellent containing a liquid-repellent compound, whereby liquid repellency can be imparted to the fibers even when the amount of water and/or a surfactant is reduced, preferably without using water and/or a surfactant.

1 . A method for producing a liquid-repellent fiber, comprising a fiber treatment of treating a fiber substrate with a repellent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium,
 wherein the liquid-repellent compound is free of a fluorine atom, wherein, with the proviso that the liquid-repellent compound has a polysiloxane group, the liquid-repellent compound has the polysiloxane group in a side chain.   
     
     
         2 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein a water contact angle of the liquid-repellent compound is 35° or more. 
     
     
         3 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound has a group represented by the following formula:
   —X—R n  
   
       wherein
 X is a direct bond or a 1+n valent group, 
 R is independently at each occurrence an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, or a polysiloxane group, and 
 n is 1 or more and 3 or less. 
 
     
     
         4 . The method for producing a liquid-repellent fiber according to  claim 3 , wherein R is an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and R has 12 or more carbon atoms. 
     
     
         5 . The method for producing a liquid-repellent fiber according to  claim 3 , wherein X is a 1+n valent group composed of one or more selected from the group consisting of
 X 1  composed of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —S(═O) 2 —, —NR′—, —C(OR′)R′—, and —C(OR′)(—) 2 , wherein R′ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and   X 2  which is a hydrocarbon group having 1 to 40 carbon atoms.   
     
     
         6 . The method for producing a liquid-repellent fiber according to  claim 3 , wherein X is a group represented by
   —X 1 — or
     —X 1 —X 2 —X 1 —
   
       wherein
 X 1  is independently at each occurrence 
 a direct bond; 
 —O—; 
 —O—C(═O)—; 
 —O—C(═O)—O—; 
 —O—C(═O)—NR′—; 
 —NR′—; 
 —NR′—C(═O)—; 
 —NR′—C(═O)—O—; 
 —NR′—C(═O)—NR′—; 
 —C(═O)—; 
 —C(═O)—O—; 
 —C(═O)—NR′—; 
 —SO 2 —; 
 —SO 2 NR′—; 
 —C(OR′)R′— or 
 —C(OR′)(—) 2    
 wherein 
 R′ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and 
 X 2  is a hydrocarbon group having 1 to 40 carbon atoms. 
 
     
     
         7 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound has a repeating unit derived from a compound represented by the following formula:
   CH 2 =C(-Q)-C(═O)—X—R n  
   
       wherein
 Q is a hydrogen atom, a monovalent organic group, or a halogen atom; 
 X is a 1+n valent group composed of one or more selected from the group consisting of
 X 1  composed of one or more selected from the group consisting of a direct bond, —O—, —C(═O)—, —S(═O) 2 —, —NR′—, —C(OR′)R′—, and —C(OR′)(—) 2 , wherein R′ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and 
 X 2  which is a hydrocarbon group having 1 to 40 carbon atoms; R is an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent; and 
 
 n is 1 to 3. 
 
     
     
         8 . The method for producing a liquid-repellent fiber according to  claim 7 , wherein X is a group represented by the following formula:
   —X 1 — or —X 1 —X 2 —X 1 —
   
       wherein
 X 1  is independently at each occurrence —O—, —NR′—, —C(═O)—NR′—, —NR′—C(═O)—, or —NR′—C(═O)—NR′—, wherein R′ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; and X 2  is a hydrocarbon group having 1 to 40 carbon atoms. 
 
     
     
         9 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound is a compound in which one or more base material compounds selected from the group consisting of a monosaccharide, a polysaccharide, an alcohol, a polyol, a carboxylic acid, a polyvalent carboxylic acid, and derivatives thereof are modified with a group represented by the following formula:
   —X—R n  
   
       wherein
 X is a direct bond or a 1+n valent group, 
 R is independently at each occurrence an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and 
 n is an integer of 1 to 3. 
 
     
     
         10 . The method for producing a liquid-repellent fiber according to  claim 9 , wherein the base material compound is one or more selected from the group consisting of starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, gellan gum, tamarind seed gum, cycloamylose, glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stevioside, dextrin, cyclodextrin, glycerin, polyglycerin, menthol, xylitol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine, catechin, anthocyanin, quercetin, citric acid, malic acid, gluconic acid, alginic acid, butyric acid, lactic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, chlorogenic acid, aldonic acid, uronic acid, aldaric acid, phytic acid, ascorbic acid, and derivatives thereof. 
     
     
         11 . The method for producing a liquid-repellent fiber according to  claim 9 , wherein the base material compound is a glycerin polymer or a citric acid polymer. 
     
     
         12 . The method for producing a liquid-repellent fiber according to  claim 9 , wherein the base material compound has a hydroxy group, and
 the hydroxy group forms a group represented by the following formula:   —O—;   —O—C(═O)—;   —O—C(═O)—NR′— or   —O—C═S—NR′—   wherein R′ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,   in the liquid-repellent compound.   
     
     
         13 . The method for producing a liquid-repellent fiber according to  claim 9 , wherein the base material compound has a carboxyl group, and
 the carboxyl group forms a group represented by   the following formula:   —C(═O)—;   —C(═O)—O—;   —C(═O)—NR′— or   —C(═O)—S—   wherein R′ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms,   in the liquid-repellent compound.   
     
     
         14 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound is a compound represented by the following formula:
   A(-X—R n ) m  
   
       wherein
 A is an m valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring optionally having a substituent; 
 X is independently at each occurrence a direct bond or a 1+n valent group; 
 R is independently at each occurrence an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent; 
 n is independently at each occurrence 1 or more and 3 or less; and 
 m is 1 or more and 6 or less. 
 
     
     
         15 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound is a compound obtained by polymerizing a compound represented by the following formula:
   A(-X—R n ) m  
   
       wherein
 A is an m valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocyclic ring optionally having a substituent; 
 X is independently at each occurrence a direct bond or a 1+n valent group; 
 R is independently at each occurrence an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent; 
 n is independently at each occurrence 1 or more and 3 or less; and 
 m is 1 or more and 6 or less, 
 via a substituent of A. 
 
     
     
         16 . The method for producing a liquid-repellent fiber according to  claim 14 , wherein X is a group represented by the following formula:
   —X 1 — or
     —X 1 —X 2 —X 1 —
   
       wherein
 X 1  is independently at each occurrence 
 a direct bond; 
 —O—; 
 —O—C(═O)—; 
 —O—C(═O)—O—; 
 —O—C(═O)—NR′—; 
 —NR′—; 
 —NR′—C(═O)—; 
 —NR′—C(═O)—O—; 
 —NR′—C(═O)—NR′—; 
 —C(═O)—; 
 —C(═O)—O—; 
 —C(═O)—NR′—; 
 —C(OR′)R′— or 
 —C(OR′)(—) 2    
 wherein R′ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and 
 X 2  is a hydrocarbon group having 1 to 40 carbon atoms. 
 
     
     
         17 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound. 
     
     
         18 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound has a polysiloxane group. 
     
     
         19 . The method for producing a liquid-repellent fiber according to  claim 18 , wherein the liquid-repellent compound has the polysiloxane group in a side chain. 
     
     
         20 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the liquid-repellent compound is an amine modified product having:
 an amine backbone; and   one or more aliphatic hydrocarbon-containing groups represented by the following formula:
   —X N —R n  
 
   wherein   X N  is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 or more and to 40 or less carbon atoms and optionally having a substituent, and   n is an integer of 1 or more and 3 or less,   wherein at least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine backbone.   
     
     
         21 . The method for producing a liquid-repellent fiber according to  claim 20 , wherein the amine backbone is composed of a monovalent to trivalent amino group and a chain saturated aliphatic hydrocarbon group or aromatic hydrocarbon group optionally interrupted by an oxygen atom and/or a sulfur atom. 
     
     
         22 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein the fiber is a polyester or polyester blended fiber. 
     
     
         23 . The method for producing a liquid-repellent fiber according to  claim 1 , wherein a water concentration in a treatment agent for treating the fiber substrate is 0.001 mol/L or less. 
     
     
         24 . A composition comprising the liquid-repellent compound defined in  claim 1  and supercritical carbon dioxide. 
     
     
         25 . A repellent comprising the liquid-repellent compound defined in  claim 1  and supercritical carbon dioxide. 
     
     
         26 . A fiber subjected to water-repellent treatment with a composition or repellent comprising the liquid-repellent compound defined in  claim 1  and supercritical carbon dioxide.