WO2003016612A1

WO2003016612A1 - Textile treatment

Info

Publication number: WO2003016612A1
Application number: PCT/JP2001/007033
Authority: WO
Inventors: Tadasi Tanaka; Tetuya Takasu
Original assignee: Sanyo Chemical Industries, Ltd.
Priority date: 2001-08-15
Filing date: 2001-08-15
Publication date: 2003-02-27
Also published as: CN1267602C; CN1553978A

Abstract

Textile treatments, are disclosed, comprising an aqueous dispersion containing a blocked polyurethane (A) of an NCO-terminated prepolymer blocked with a bisulfite, and a hydrophobic solvent (B) having a water-solubility of at most 2 and/or an electrolyte (C) having a molar conductance (Μ) of 110 - 130 S.cm2/mole.Treatments containing (B) are stable even at a lower temperature.Treatments containing (C) show low migration of resins and provide textile products of soft feelings with improved shrink-resistance.

Description

DESCRITPION

TEXTILE TREATMENT

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a textile treatment. More particularly, it relates to a textile treating composition useful for finishing textile materials such as textiles and nonwoven fabrics.

2. Description of the Prior Art

There has been heretofore known a textile treating agent (hereinafter referred to as treatment) , comprising an aqueous dispersion of a polyurethane prepolymer blocked with a bisullfite (such as JP-A-2000-265374) .

It has also been proposed to carry out afterward dipping of a textile material treated with a polyurethane into an aqueous solution of an electrolyte to inhibit migration of a polyurethane therefrom (such as JP-A-H6- 33397) .

SUMMARY OF THE INVENTION It is an object of the present invention to provide a treatment stable even under low temperature.

It is another object of this invention to provide a treatment capable of preventing or reducing migration of a treated resin.

Briefly, these and other objects of the present invention as hereinafter will become more readily apparent have been attained broadly by a treatment, which comprises an aqueous dispersion containing:

(A) a blocked polyurethane of an NCO-terminated urethane prepolymer (a) blocked with a bisulfite (b) , and

(B) a hydrophobic solvent, and/or (C) an electrolyte.

(B) has a water-solubility (hereinafter referred to as S) , g/lOOg water at 25°C , of at most 2.

(C) is a salt of a strong acid having a pKa of not more than 2, and has a molar conductance (Λ ), of 0.01 mole % aqueous solution at 25°C , in the range of 110-130

S • cm²/mole .

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hydrophobic Solvent (B)

Suitable hydrophobic solvents (B) include, for example, hydrophobic alcohols (Bl) , esters (B2), ethers

(B3), ketones (B4), hydrocarbons (B5), and halogenated hydrocarbons (B6) .

(Bl) Suitable alcohols include ones of C6-18, preferably C6-12 especially C6-9. In the above and hereinafter, C represents the number of carbon atoms. Examples of (Bl) are : (Bll) monohydric alcohols, including aliphatic ones (Bill), for instance, straight-chain and branched alkanols, including natural ones and synthetic ones (e.g. Ziegler alcohols and oxo alcohols) , such as 2-ethyl- butanol, 2- and 4-methyl-pentanols, 1-hexanol, 2-ethyl- pentanol, 2-methyl-hexanol, 1-, 2- and 3-heptanols (hereinafter referred to as HP), 2-ethyl-hexanol, 1- and 2- octanols, 1-nonanol, decanol, undecanol, dodecanoi and tridecanol; and unsaturated alcohols, including alkenols and alkadienols, such as 2-propylallylalcohol, 2-methyl- pentenol, 1-hexenol, 2-ethyl-4-pentenol , 2-methyl-5- hexenol, 1-heptenol, 2-ethyl-5-hexenol, 1-octenol, 1- nonenol, undecenol, dodecenol and geraniol; cycloaliphatic ones (B112), including cyclo-alkanols and cycloalkenols , such as methylcyclohexanol and a -terpineol; and aromatic ones (B113), such as phenethyl and salicyl alcohols; as well as (B12) dihydric alcohols, for example, alkanediols, such as 1,6-hexane, 1,8-octane and 1 , 12-dodecane-diols .

Among these, preferred in view of dispersibility into aqueous dispersions are monohydric alcohols (Bll), particularly (Bill).

(B2) Suitable esters include hydrocarbyl esters (B21) of C4-24, preferably C6-12, especially C6-8; and polyol esters (B22) of C4-60, preferably C6-30, especially C6-24.

Hydrocarbyl esters (B21) are inclusive of hydrocarbyl carboxylates , such as hydrocarbyl monocarboxylates (B211) and mono- and di-hydrocarbyl dicarboxylates (B212). In the above and hereinafter, hydrocarbyl groups mean monovalent hydrocarbon groups, including (cyclo) aliphatic ones, such as (cyclo) alkyl and (cyclo) lkεnyl groups, and aromatic ones, such as (alkyl) aryl and aralkyl groups; and (cyclo) aliphatic represents aliphatic and/or cycloaliphatic, and similar expressions are used hereinafter. Hydrocarbyl alcohols include (Bll) and lower alcohols, for example, aliphatic monohydric alcohol (Cl-5) (alkanol or aikenol : such as methyl, et-hyi, n- and i-propyi, n-, i-, sec- and t-butyl, pentyl, vinyl and (meth)allyl alcohols, and benzyl alcohol.

Suitable monocarboxylic acids constituting (B211) include straight-chain and branched, saturated and unsatur- ated carboxylic acids (fatty acids) of C2-20, such as acetic, propionic, butyric, octanoic, 2-ethylhexanoic , lauric, palmitic, myristic, stearic, abietic, (meth) - acrylic, (iso) crotonic , oleic and linoleic acids and tall oil fatty acids.

Examples of (B211) are esters of a hydrocarbyl alcohol with a monocarboxylic acid as above, for example, alkyl and alkenyl acetates, such as n-butyl acetate (hereinafter referred to as BuAc) , isoamyl, hexyl, octyl, dodecyl, octadecyl, vinyl, octenyl and dodecenyl acetates; corresponding propionates, butyrates and stearates, such as butyl and hexyl propionates, hexyl butyrate and butyl stearate; and methyl and butyl methacrylates . Suitable dicarboxylic acids constituting (B212) include saturated and unsaturated dicarboxylic acids (C4- 8) , as described below in (i3) . Illustrative of (B212) are mono- and di-hydrocarbyl esters C esters of (Bll) or a lower alcohol] of a dicarboxylic acid as above, for examples, mono- and di-alkyl succinates, such as mono- and di-2-ethyl-hexyl, mono- and di-dodecyl, dimethyl and diethyl succinates; ono-and di-alkyl glutarates, such as dimethyl glutarate; and mono-and di-alkyl adipates, such as mono- and di-methyl adipates.

Suitable polyols constituting (B22) include polyhydric alcohols, for example, straight-chain and branched aliphatic diols, including alkanediols (C2-12), such as ethylene glycol, 1,2- and 1 , 3-propylene glycols, 1,2-, 2,3-, 1,3- and 1,4-butylene glycols, neopentyl glycol and 1,6-hexylene glycol (hereinafter referred to as EG, PG, BG, NPG and HG, respectively), 1 , 5-pentanediol , 3- methyl-1 , 5-pentanediol , 2-methyl-2 , 4-pentanediol, 2,2- diethyl-1 , 3-propanediol, 1 , 8-octanediol and 1 , 12-dodecane- diol; cycloaliphatic diols, including those disclosed in US Patent 4,990,545, such as cyclohexanediol , cyclohexane- dimethanol; and aromatic diols, such as xylenediol; as well as polyols having a higher functionality (3-8) , for example, alkane polyols and intermolecular and intramolecular dehydrates thereof, such as glycerol, 1,2,6- hexane-triol, trimethylolpropane (hereinafter referred to as TMP) , pentaerythritol, sorbitol, polyglycerols (poly- merization degree:2-8), dipentaerythritol and sorbtan, sugars and derivatives thereof (glycosidεs) , such as sucrose and methylglucoside; and (poly) oxyalkylene polyols having oxyalkylene (C2-12) groups, for instance, poly- alkylene glycols, such as diethylene glycol, triethylene glycol and dipropylene glycol (hereinafter referred to as DEG, TEG and DPG, respectively) , and polyoxyalkylene polyols, such as alkylene oxide (hereinafter referred to as AO) adducts of an initiator (i) containing 2-8 active hydrogen atoms as described below (e.g. alkane polyols as above) .

Suitable AOs, used in producing the above adducts and (B32) and (a211) below, include, for example, ethylene oxide (hereinafter referred to as EO) , propylene oxide (hereinafter referred to as PO) , 1,2-, 2,3- and 1,3- butylene oxides, tetrahydrofuran (hereinafter referred to as THF) , iso-butylene oxide, a -olefin oxides (C5-12 or more) , and substituted AOs such as styrene oxide and epihalohydrins (e.g. epichlorohydrin) , as well as combinations of two or more of AOs (block and/or random addition) .

Exemplary of (B22) are mono- and poly-esters of a polyol as with a monocarboxylic acid as above, for instance, HG mono- and di-acetates; EG mono- and di-2- ethylhexanoates; NPG mono- and di-2-ethyl-hexanoates ; TMP mono-,di- and tri-2-ethylhexanoates ; and mono-, di- and tri-fatty acid (C12-18) esters of sorbitan having an HLB (Oda's HLB, as described below) of 1-7.

Among these, preferred in view of dispersibility into aqueous dispersions are hydrocarbyl esters (B21), particularly monocarboxylates (B211). More preferred are aliphatic carboxylic acid alkyl esters, especially BuAc . (B3) Suitable ethers include hydrocarbyl ethers (B31), of C5-18, preferably C6-12, especially C6-8 and one or two ether linkages, and polyalkylene ethers (B32) having 2-60 oxyalkylene groups and a number-average molecular weight (hereinafter referred to as Mn) , determined by GPC (gel permeation chromatography) , of up to 3,000.

Examples of (B31) include (B311) dihydrocarbyl ethers, such as methyl n-pentyl ether, methyl n-octyl ether, i-propyl n-butyl ether, ethyl n-hexyl ether, di-n- butyl ether and i-butyl 2-ethylhexyl ether; (B312) mono- and poly-hydrocarbyl ethers of polyols [ as mentioned in (B22)] , for example, EG mono- and di-2-ethylhexyl ethers, EG mono- and di-decyl ethers, BG mono- and di-2-ethylhexyl ethers, HG mono- and di-i-butyl ethers, HG mono- and di- pentyl ethers, and TMP mono-, di- and tri-2-ethylhexyl ethers .

Polyalkylene ethers (B32) include (poly) oxyalkylene polyols (B321), having oxyalkylene (C3-12) groups; hydrocarbyl ethers (B322) of a (poly) oxyalkylene polyol having oxyalkylene (C2-12) groups; and esters (B323) of a monocarboxylic acid as mentioned above in (B21) with a (poly) oxyalkylene polyol having oxyalkylene (C2-12) groups or a partial hydrocarbyl ether thereof.

Suitable (poly) oxyalkylene polyols (B321) include hydrophobic ones among (poly) oxyalkylene polyols mentioned in (B22) . Illustrative of (B321) are polyalkylene glycols (hereinafter referred to as PAG) , such as polypropylene glycol (hereinafter referred to as PPG; Mn 800-3,000); polytetramethylene ether glycol (hereinafter referred to as PTMG; Mn 300-700) ; and block and random copolymers (Mn 500-1,000) of PO and THF; and polyoxypropylene triols (Mn 800-3,000), such as PO adduct-s of glycerol and of TMP .

Suitable (poly) oxyalkylene polyols in (B322) and (B323) include the same ones as in (B22). Examples of (B322) include mono- and di-alkyl (Cl-4) ethers of the above PAG, AO (such as EO, PO and/or THF) adducts of a monohydric alcohol as mentioned in (Bll), coupled products of these monoether and/or AO adduct through an alkylene dihalide (Cl-4; such as methylene dichloride) ; mono-, di- and tri-alkyl (Cl-4) ethers of the above polyoxypropylene triols; and mono- and di-alkyl (C8-18) ethers of a polyethylene glycol (hereinafter referred to as PEG; Mn 106-370), such as EO (2-8 moles) adducts of a fatty alcohol (C10-24) having an HLB (Oda's) of 1-7, DEG di-2- ethylhexyl ether and TEG distearyl ether. Exemplary of (B323) are mono- and di-acetates of the above PAG; mono-, di- and tri-acetates of the above polyoxypropylene triols; mono-acetates of the above monoalkyl ethers and dialkyl ethers of polyoxypropylene triols; diacetates of the above monoalkyl ethers of polyoxypropylene triols; 2- ethylhexanoates corresponding to these acetates; and di- esters of a monocarboxylic acid (C8-18) with PEG (Mn 106- 300), such as DΞG di-2-ethylhexanoate and TEG distearate. Among these, preferred in view of dispersibility into aqueous dispersions are hydrocarbyl ethers (B31) particularly (B312), especially glycol monoalkyl ethers. (B4) Suitable ketones include ones of C4-24, preferably C6-12, especially C6-8 in total. Illustrative of (B4) are dihydrocarbyl ketones, for example, aliphatic dihydro- carbyl (alkyl and/or alkenyl) ketones, such as methyl i- butyl ketone (hereinafter referred to as MIBK) , di-i- propyl ketone, methyl amyl ketone, ethyl i-butyl ketone, di-i-butyl ketone, i-butyl isoamyl ketone, di-isoamyl ketone, i-butyl allyl ketone, i-propyl allyl ketone, ethyl octenyl ketone and diallyl ketone; and cyclic ketones, such as cyclohexanone . Among these, preferred are aliphatic ketones, particularly dialkyl ketones (MIBK). (B5) Suitable hydrocarbons include ones of C4-24, preferably C6-12, especially C6-8. Illustrative of (B5) are (cyclo) aliphatic ones (B51), for example, straight- chain and branched alkanes, such as n-hexane, n- and i- octanes, n-nonane, and n- and i-decanes; alkenes, such as 1- and 2-octenes, 1-nonene, 1-decene and 1-dodecene; cycloalkanes, such as cyclohexane, cyclodecane and cyclododecane; and cycloalkenes, such as cyclohexene and cyclododecene; and aromatic ones (B52), for instance, benzene, toluene, xylene, cumene, ethylbenzene and styrene .

(B6) Suitable halogenated hydrocarbons include ones of C4-24, preferably C6-12, especially C6-8 and containing 1-4 halogen atoms (such as chlorine, bromine and iodine). Examples of (B6) include aliphatic ones (B61) , such as dichloromethane , chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloropropane; and aromatic ones (662), such as chlorobenzene, brorαobenzene, dichlorobenzene and benzyl chloride.

Among these solvents (B) , preferred are (Bl), (B2) , (B3) and (B4) .

(B) is preferably liquid at ordinary temperature, for handleability. It is preferred that (B) has a boiling point, under normal pressure, of not more than 240°C , particularly not more than 220°C , in view of easy removability through distillation from treated textile materials .

(B) is used to reduce solubility of (A) towards aqueous medium (hereinafter referred to as AMS) , g/lOOg aqueous medium at 25°C . For instance, upon adding (B) to (A) having an AMS of 20-100, there can be attained an aqueous dispersion having such a reduced AMS of 1-10.

Electrolyte (C)

Electrolyte (C) is a salt of a strong acid having a pKa of not more than 2, in view of providing sufficient effects of preventing or reducing migration of a polyurethane resin. In the above, pKa means logarithm of reciprocal of dissociation constant (Ka) of the acid, as measured at 25°C in infinite dilution aqueous solution, and equals to -logKa.

(C) has a molar conductance (Λ ), of 0.01 mole % aqueous solution at 25^CC , in the range of 110-130, preferably 110-120 S* cm²/mole, for providing sufficient effects of preventing or reducing migration of a polyurethane resin, without causing deposition of the resin within the treatment or onto squeezer rolls such as mangles. The symbol S in the unit of Λ represents Siemens, which is a unit of conductance.

Suitable strong acids and pKa values thereof and values of molar conductance (Λ ) of salts are written respectively in pages 11-317 and 11-322 and in pages II- 446 to 451, of "Chemical Handbook" Fundamental Chapter II, Revised 4th edition (published 1993, by Chemical Society of Japan) . Measurement of Λ may also be carried out with a conductivity meter, "DS-15" produced by Horiba-seisaku- sho, using a conductivity electrode plated with platinum black, at 25± 0.2°C .

Examples of suitable strong acids include HCl (ρKa=-8), HBr (pKa=-9), HI (pKa=-10), HN0₃ (pKa=-1.8), H2SO4 (pKa₂=1.99), H₂S₂0₃ (pKa₂=1.6), HI0₃ (pKa=0.77), phosphinic acid HPH₂0₂ (pKa=1.23) and H₂Se0₄ (pKa₂=1.70).

Suitable salts include (Cl) metallic salts: including (Cll) salts of alkali (IA) metals (such as Li, Na and K) , and (C12) salts of other metals, for instance, IB metals (such as Cu and Ag) , alkaline earth (IIA) metals

(such as Mg, Ca, Sr and Ba) and IIB metals (such as Zn) ; and (C2) metal-free salts: including (C21) ammonium salts, and (C22) salts of organic bases, for example, (C221) salts of primary, secondary and tertiary amines and (C222) quaternary ammonium salts.

Exemplary of (Cl) are (Cll): Na₂S0₄, K₂S0₄, NaN0₃ , NaCl, NaBr, Nal , Na₂S₂0₃ and the like; and (C12): Sr(N0₃)₂, Ba(N0₃)₂, Ca(N0₃)₂, AgN0₃ , Mg(N0₃)₂, Zn(N0₃)₂, Cu(N0₃)₂, Mg(Cl)₂, Ca(Cl)₂, Sr(Cl)₂, Ba(Cl)₂, Cu(Cl)₂ and the like.

Suitable amines forming (C221) include, for example, mono-, di- and tri-hydrocarbyl (Cl-20) and/or hydroxyalkyl (C2-4) amines: including monoalkyl amines

(Cl-18) , such as methyl, ethyl, n-propyl, n- and i-butyl, n-hexyl and n-octyl amines; dialkyl amines (C.2-20) , such as dimethyl, diethyl, dibutyl, dioctyl, methylbutyl, ethyl- butyl and methylpentyl amines; trialkyl and dialkylbenzyl amines (C2-18), such as trimethyl, triethyl, tributyl, dimethylethyl , dimethylbutyl , dimethylbenzyl and diethyl- benzyl amines; alkanol amines, such as mono-, di- and tri- ethanol amines and iso-propanol amines, ethylethanol amine and diethylethanol amine; amidine compounds, for example, N,N,N' -hydrocarbyl-substituted amidines (such as N,N- dimethyl-N' -benzyl ormamidine) , and cyclic amidines, such as imidazoles (e.g. 1-methylimidazole and 1-methylbenz- imidazole) , imidazolines (e.g. 1 , 2-dimethylimidazoline) , tetrahydropyrimidines (e.g. 1 , 2-dimethyl-l , 4 , 5 , 6-tetrahydropyrimidine) and diazabicycloalkenes (e.g. 1,8-diaza- bicyclo [ 5.4.01 undecene-7 and 1 , 5-diazabicyclo [ .3.0 ] nonene-5), as mentioned in WO 95/15572.

Suitable quaternary ammonium salts of (C222) include ones obtainable by quaternization of these amines and amidine compounds with a quaternizing agent. Examples of suitable quaternizing agents are ones having alkyl or aralkyl group (Cl-11), such as alkyl halides, benzyl halides, dialkyl sulfates and dialkyl carbonates, and epoxy group-containing compounds, such as AO (C2-4), as described in WO 95/15572.

Illustrative of (C2) are (C21) : NH₄C1, NH₄N0₃ , NH₄S0₄ and the like; and (C221) : 2-hydroxyethylammonium chloride H0-CH₂CH₃-NH₂ • HC1 , dimethylammonium chloride N(CH₃)_2'HC1, trimethylammonium chloride N(CH₃)_3'HC1 and the like; and (C222): methyl- triethylammonium chloride CH₃N"^*" (C₂H₅) 3 ' Cl^~ , tetraethyl- ammonium chloride N"^*" (C₂H₅ ) ₄ ' Cl- , methyl-quaternized 1- methylimidazole chloride, methyl-quaternized 1-methylbenz- imidazole chloride, methyl-quaternized 1 , 2-dimethylimidazoline chloride, methyl-quaternized 1 , 2-dimethyl- 1 , 4 , 5 , 6-tetrahydropyrimidine chloride, methyl-quaternized 1 , 8-diaza-bicyclo [5.4.0 ] undecene-7 chloride and methyl- quaternized 1 , 5-diazabi-cyclo [4.3.0] nonene-5, and corresponding nitrates, sulfates and methosulfates . Among these salts, preferred are metallic salts (Cl). More preferred are (Cll) (especially Na₂S0₄ and K₂S0₄) and combination thereof with (C12). Preferable content of (Cll) in (Cl) is at least 50 %, particularly at least 80 %, in view of providing suffecient effects for preventing or reducing migration of a treated polyurethane resin.

In the above and hereinafter, % and parts represent % by weight and parts by weight, respectively, unless otherwise specified.

Blocked Polyurethane (A)

(a) NCO-terminated Urethane Prepolymer

NCO-terminated urethane prepolymer, hererinafter abbreviated as prepolymer (a) , to be blocked with a bisullfite (b) is obtainable by reacting an organic poly- isocyanate (al) with an active hydrogen atom-containing component comprising a polyol (a2).

Suitable organic polyisocyanates (al) include :

(all) aromatic polyisocyanates (C6-20, except carbon atoms in NCO groups), such as 1,3- and/or 1 , 4-phenylene diiso- cyanates, 2,4- and/or 2,6-tolylene diisocyanates (TDI), crude TDI, diρhenylmethane-2 , 4 ' - and/or -4 , 4 ' -diisocyanates (MDI) , crude MDI [phosgenated products of crude diaminophenylmethane {condensation products of an aromatic amine (aniline) or mixtures thereof with formaldehyde : mixtures of diaminodiphenylmethane with minor amount (such as 5-20 %) of polyamines of 3 or more functionality}; polyarylpolyisocyanates I , naphthylene-1 , 5-diisocyanate, triphenylmethane- , 4 ' , 4"-triisocyanate, and m- and p- isocyanatophenyl sulfonylisocyanate ;

(al2) aliphatic polyisocyanates (C2-18), such as ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDD , dodeca- methylene diisocyanate, 1 , 6 , 11-undecane triisocyanate, 2 , 2 , 4-trimethylhexane diisocyanate, lysine diisocyanate, 2 , 6-diisocyanatomethyl caproate, bis ( 2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2 , 6-diisocyanatohexanoate;

(al3) alicyclic polyisocyanates (C4-15) , such as iso- phorone diisocyanate (IPDI) , dicyclohexylmethane diisocyanate (hydrogenated MDI) , cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) , and bis ( 2-isocyanatoethyl) 4-cyclohexene-l , 2-dicarboxylate; (al4.) araliphatiσ polyisocyanates (C8-15), such as xylylene diisocyanates ; and

(al5) modified polyisocyanates (such as modified products containing urethane, carbodiimide , allophanate, urea, biuret, urethdione, urethonimine , isocyanurate and/or oxazolidone groups) of (all) - (al4), having an equivalent weight (molecular weight per functional group: hereinafter referred to as EW) , determined NCO-content, of usually 130- 280, preferably 145-230, for example, modified MDIs (e.g. urethane- and/or carbodiimide-modified MDIs and trihydro- carbyl phosphate-modified MDI), modified TDIs (e.g. urethane-modified TDIs) , modi-fied HDIs (e.g. urethane-, biuret- and/or isocyanurate-modified HDIs) and modified IPDIs (e.g. urethane- and/or isocyanurate-modified IPDIs) ; as well as mixtures of two or more of them, such as combinations of modified MDI with urethane-modified TDI. Polyols, used for producing urethane-modified polyisocyanates, include polyols having an EW (determined by hydroxyl number) of 30-200, for example, diols (such as EG and PG) and polyols having 3-8 or more hydroxyl groups (such as TMP) , as mentioned in (B22), and AO (EO and/or PO) adducts thereof (such as DEG, DPG and PO adducts of TMP) .

Diisocyanates are preferred among polyisocyanates.

Among these polyisocyanates, preferred are non- aromatic polyisocyanates of (all) - (al4), including (al5) derived therefrom, to provide treated textile materials of non-discolouring or non-yellowing properties. More preferred are (al2), in view of feeling of treated fabrics.

Active hydrogen atom-containing component to form prepolymer (a) comprises a polyol (a2). Suitable polyols (a2) include high molecular weight (hereinafter referred to as MW) polyols (a21) having an EW (determined by hydroxyl number) of at least 400, preferably 500-2,000, particularly 600-1,700; for example, polyether polyols (a211), polyester polyols (a212) and hydroxyl-containing vinyl polymers (a213). Polyols (a2) may comprise a low MW polyol (a22) having an EW (determined by hydroxyl number) of less than 400, in addition to or instead of (a21).

Polyether polyols (a211) include ones of the structure obtainable by addition of one or more AOs to an initiator (i) containing at least two (preferably 2-8) active hydrogen atoms .

AOs include those (C2-12 or more) mentioned above. Preferred are PO, and combinations of PO with other AO (such as EO) . PO is preferably contained in an amount of at least 30 %, based on the total weight of AOs.

Suitable initiators (i) include : (il) polyhydric alcohols, for example, diols (such as EG and PG) and polyols having 3-8 or more hydroxyl groups (such as TMP), as mentioned in (B22); (i2) polyhydric phenols, for instance, mononuclear polyhydric phenols (di- and trihydric phenols such as hydroquinone, resorcinol, pyrocatechol, phloroglucinol and pyrogallol) , bisphenols (such as bisphenol A, bisphenol F and bisphenol S; and halogenated products as disclosed in US Patent 4,990,545, e.g. tetrabromobisphenol A), and phenol-formaldehyde condensation products (novolak and resol) ;

(i3) (hydroxy) carboxylic acids, including polycarboxylic acids (i31), having 2-8 or more carboxyl groups, for example, aliphatic polycarboxylic acids (C2-40), including saturated ones, such as oxalic, malonic, succinic, glu- taric, adipic, ethylsuccinic, pymeric, suberic, azelaic, sebacic and dodecanedicarboxylic acids, and unsaturated ones, such as maleic, fumaric, itaconic, citraconic and mesaconic acids, and polymers (polymerization degree: 2-8) of unsaturated carboxylic acids [ (meth) acrylic and (iso) crotonic acids, unsaturated polycarboxylic acids as above, and the like] , such as dimers of maleic and itaconic acids, and pentamers of (meth) acrylic acids; alicyclic polycarboxylic acids (C7-60) , such as 1,2- and 1 , 3-cyclopentanedicarboxylic , 1,2-, 1,3- and 1,4-cyclo- hexanedicarboxylic and 1 , 2 , 2-trimethyl-l , 3-cyclopentanedicarboxylic acids, and polymerized fatty acids [dimer and trimer acids of unsaturated fatty acids (such as linolenic and linoleic acids)] ; and aromatic polycarboxylic acids (C8-12), such as aromatic dicarboxylic acids, e.g. (iso) phthalic , terephthalic and naphthalene- dicarboxylic acids, and benzenetricarboxylic and benzene- tetracarboxylic acids (e.g. trimellitic and pyromellitic acids); hydroxycarboxylic acids (i32), for example, aliphatic ones, such as glycolic, lactic, glyceric, tartronic, malic, tartaric and ricinoleic acids, and aromatic ones, such as tropic, salicylic and p-hydroxy- benzoic, 3 , 4-dihydroxybenzoic and gallic acids; (i4) amines, including primary monoamines (i41), for example, monohydrocarbyl (Cl-20) amines, such as monoalkyl amines as mentioned in (C221), benzylamine and aniline, alkanol (C2-4) amines as mentioned in (C221); and polyamines (i42) having 2-10 amino groups, for example, aromatic polyamines (C6-20), aliphatic polyamines (C2-18), alicyclic polyamines (C4-15) and araliphatic polyamines (C8-15) , corresponding to (all), (al2), (al3) and (al4), respectively, NCO groups thereof having been substituted with amino groups, such as tolylene diamines, diaminodiphenylmethane, crude diaminophenylmethane (polymethylene- polyphenylene polyamine) , alkylene diamines (C2-6; e.g. ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine), isophorone diamine, dicyclohexylmethane diamines and xylylene diamines; polyalkylene (C2-6) polyamines, such as diethylene triamine, triethylene tetramine and dipropylene triamine; hetero- cyclic polyamines, such as piperazine and aminoalkyl (2-6) piperazines (e.g. aminoethylpiperazine) ; and partially alkyl (Cl-8) -substituted products of these polyamines, including N-alkyl-substituted polyamines, such as N- methylaminoethylamine, and nuclear-substituted aromatic polyamines, such as mono- and di-alkyl (Cl-8) -tolylene diamines;

(i5) polythiols, for instance, ones corresponding to (il), such as ethylene, propylene, 1,4-butane and dodecane dithiols ;

(i6) phosphorus-containing acids, for example, phosphoric acids (such as phosphoric, pyrophosphoric and polyphos- phoric acids), phosphorous, phosphonic and phosphinic acids, and partial alkyl (Cl-8) esters of these acids (such as dibutyl pyrophosphate) ; and the like.

Among these, preferred are polyhydric alcohols (il) particularly aliphatic ones. Among polyhydric alcohols, more preferred are trihydric alcohols and particularly dihydric alcohols.

Polyether polyols (a211) are obtainable by ring- opening addition polymerization of one or more AOs to an initiator (i) in the presence of a catalyst. Suitable calalysts include, for example, anionic addition polymerization catalysts, cationic addition polymerization catalysts and coordination anionic addition polymerization catalysts. Preferred are anionic addition polymerization catalysts, such as alkali metal hydroxides (e.g. sodium, potassium and cesium hydroxides) . Addition polymerization can be carried out at a temperature of usually 40-150°C , preferably 90-130°C . Polyether polyols (a211) may also be obtained by coupling two moles or more of AO adducts thus obtained with a coupling agent, such as an alkylene dihalide (Cl-4; e.g. methylene dichlo.ride) .

Illustrative of (a211) are polyoxyalkylene diols, such as PPG, PTMG and AO (PO and/or EO) adducts of bisphenol A, and branched polyoxyalkylene polyols, such as AO (PO and/or EO) adducts of glycerol.

Polyester polyols (a212) are inclusive of condensation polyester polyols (a2121), obtainable from a polyol with a polycarboxylic acid; polylactone polyols (a2122), obtainable by ring-opening polymerization of a lactone in the presence of a polyol; castor oil polyols (a2123), including castor oil and transesterified products thereof with a polyol; and polycarbonate polyols (a2124), obtainable by ring-opening polymerization of an alkylene carbonate in the presence of a polyol.

Suitable polyols used in (a2121), (a2122) , (a2123) and (a2124) include polyhydric alcohols (il) and polyoxyalkylene polyols (including (a211), and adducts of lower moles of AO to an initiator (i)] .

Suitable polycarboxylic acids in (a2121) include ones mentioned in (i31); among which preferred are dicarboxylic acids, particularly aliphatic dicarboxylic acids, such as adipic acid. Among polyols, preferred for use in (a2121) are polyhydric alcohols, particularly diols (such as EG, DEG, BG,HG and NPG) and combination thereof with a minor amount (20 % or less, preferably 10% or less) of polyols having 3-4 hydroxyl groups (such as TMP) . (a2121) can be obtained by reacting a polyol with a polycarboxylic acid or an ester-forming derivative thereof.

(anhydride, a halide (such as chloride) acid or a lower alkyl (Cl-4) ester] , or with a polycarboxylic anhydride and an AO . Exemplary of (a2121) are poly(EG adipate) , poly(l,4-BG adipate), poly(HG adipate), poly (NPG adipate), poly (EG/1, -BG adipate), poly(NPG/HG adipate), poly(3- methyl-pentanediol adipate) and poly (1, 4-BG isophthalate) .

Suitable lactones in (a2122) include laσtones (C4- 13), such as ε -caprolactone, δ -valerolactone and 3- methyl-c? -valerolactone. Examples of (a2l22) include poly- ε -caprolactone diols and poly-3-methyl-valerolactone dio l s .

Castor oil polyols (a2123) include castor oil, hydrogenated castor oil, low moles (such as 1-3 moles) AO adducts of castor oil, and transesterified products of castor oil with a polyol as above (EG, TMP, pentaery- thritol, etc . ) .

Suitable alkylene carbonates in (a2124) include alkylene carbonates (C3-13), such as ethylene, propylene and hexamethylene carbonates. Exemplary of (a2124) are polyethylene carbonate diol and polyhexamethylene carbonate diol.

Among these, preferred are condensation polyester polyols (a212l) .

Hydroxyl-containing vinyl polymers (a213) include polyolefinic polyols (a2131), for example, hydroxyl- terminated (co) polymers of an olefin and optionally a minor amount (such as 30 % or less, preferably 15-20 %) of a comonomer; and acrylic polyols (a2132), for example, (co)polymers of a hydroxyalkyl (C2-8) (meth) acrylate and optionally a comonomer. Suitable olefins are inclusive of alkadienes, such as 1 , 3-butadiene, and alkenes, such as a - olefins (C8-18). Suitable comono ers include, for example, aromatic hydrocarbon monomers such as styrene, unsaturated nitriles such as (meth) acrylonitriles , and alkyl (Cl-20) (meth) acrylates such as methyl (meth) acrylates . Examples of (a2131) and (a2132) are polybutadiene polyols (hereinafter referred to as PBD) , hydrogenated PBDs and poly-α - olefin polyols derived from a -olefins (C8-18), copolymers of hydroxyethyl (meth) acrylate with styrene and/or methyl (meth) acrylate, and acrylic polyols, as written in JP Patent Lay-open Nos .57413/1983 and 57414/1983.

Among these polyols (a2131) and (a2132), preferred are polyols (a2131), in view of feeling of treated fabrics .

High MW polyols (a21) may be vinyl-modified ones, so-called polymer/polyols, obtainable by polymerization of a vinyl monomer insitu within (a21) ( such as (a211) and/or (a212)] and optionally (a22). Suitable vinyl monomers include, for example, aromatic hydrocarbon monomers, such as styrene, and unsaturated nitriles, such as (meth) acrylonitriles . Polymer content in polymer/ polyols may vary widely, for instance, in an amount of generally 1-80 %, preferably 10-70 %.

High MW polyols (a211), (a212) and (a213) can be used alone or as a mixture of two or more of them.

High MW polyols (a21) generally have an average f nctionality (average number of hydroxyl groups; hereinafter referred to as F) , which can be determined by H^X-NMR, of 1.8 - 8 or more, preferably 2-4, more preferably 2.3-3, particularly 2.4-2.9, in view of preferable (not too soft and not too hard) feeling of treated fabrics.

Suitable low MW polyols (a22) include polyhydric alcohols (diols and polyols having 3-8 or more hydroxyl groups) as mentioned in (B22), and low MW AO adducts of (i) , having an EW of less than 400. In general, (a22) has an F of 2 - 8 or more, preferaly 2-3. Exemplery of (a22) are EG, PG, 1,4-BG, glycerol, TMP, bishydroxyalkylated dihydric phenol (e.g. EO 2 moles adduct of bisphenol A), bishydroxyalkylmonohydrocarbylamine (e.g. bis-hydroxyethyl- aniline) and tetrakishydroxyalkyldiamines (e.g. tetrakis- hydroxypropylethylenediamine) ; as well as adducts of low moles (1 - 8X F moles) AO (EO and/όr PO) to them.

Active hydrogen atom-containing component to form prepolymer (a) may further comprise one or more other active hydrogen atom-containing compounds (a3), including monofunctional compounds (a31) and polyfunctional compounds (a32) other than (a2).

Illutrative of suitable monofunctional (a31) are: (a311) mono-ols, for example, monohydric alcohols, such as hydrocarbyl alcohols, including (Bll) and lower alcohols as mentioned in (B211); (poly) ether mono-ols, such as cellosolves (e.g. Cellosolve, and methyl, butyl, iso-butyl and hexyl cellosolves), carbitols (e.g. Carbitol, and methyl and butyl carbitols), mono-hydrocarbyl (e.g. monoalkyl) ethers of diol and of PAG as mentioned in (B312) and (B322), respectively; and monoesters of a monocarboxylic acid with a (poly) oxyalkylene diol as mentioned in (B323); and (a312) primary and secondary monoamines, for example, mono-and di-hydrocarbyl amines (e.g. mono- and di-alkyl amines) as mentioned in (C221), and tertiary amino group-contain-ing primary and secondary monoamines, such as N,N-di- and N, N, ' -tri-hydrocarbyl-substituted products of diamines mentioned in (i4) (e.g. N,N- dimethylaminoethylamine) .

Polyfunctional compounds (a32) have an F of usually 2 - 8 or more, preferably 2-3. Exemplary of (a32) are: (a321) polyamines, for instance, aromatic, aliphatic, alicyclic and araliphatic polyamines as mentioned in (i42), and polyoxyalkylene polyamines, obtainable by cyanoalkylation (e.g. cyanoethylation with acrylonitrile) of polyether polyols of (a211) or low MW AO adducts of (a22), followed by hydrogenation of the cyano group into amino groups; and (a322) aminoalcohols , such as mono- and di-alkanol (C2-4) amines as mentioned in (C221) (e.g. mono- and di-ethanol amines and iso-propanol amines) .

Among these compounds (a3), preferred are low MW ones, having an EW (determined by active hydrogen atom- containing group number, such as hydroxyl number and primary and secondary amine number) of less than 400.

Active hydrogen atom-containing component contains (a21) in an amount of generally at least 50 %, preferably 80-99 %, particularly 90-98 %, and may contain (a22) in an amount of usually 0-50 %, preferably 1-20 %, particularly 2-10 %, and (a31) and/or (a32) in an amount of usually 0- 10 %, preferably 1-5 %, particularly 2-3 %.

In producing prepolymers (a), stoichiometrically excess of (al) is reacted with the active hydrogen atom- containing component, for instance, in such an amount providing an equivalent ratio of NCO/active hydrogen atom- containing group (the total of 0H+NH₂+NH) in the range of usually 1.3-2.2/1, preferably 1.4-2.0/1.

Equivalent ratio of (a31)/(al) is preferably 0-0.1 particularly 0-0.05. Equivalent ratio of ( (a22)+(a32)] /(al) is preferably 0-0.1 particularly 0-0.05.

Preparation of prepolymers (a) can be accomplished in a usual manner. Reaction of (al) with the active hydrogen atom-containing component may be carried out at a temperature of usually 20-150°C , preferably 60-110°C . The reaction can be carried out in the presence of or in the absence of an inert solvent. Suitable solvents include organic solvent containing no active hydrogen atom, for example, ketones, such as acetone and methyl ethyl ketone, and ethers, such as THF and dioxane .

Active hydrogen atom-containing components comrising (a21) and. optionally (a22), (a31) and/or (a32) may be reacted with (al) at one step, by admixing beforehand the components or by adding the components simultaneously; or may be reacted stepwise, for instance, by reacting (al) with (a21) followed by (a22), (a31) and/or (a32) .

Prepolymers (a) have an isocyanate content (hereinafter referred to as NCO%) of generally 0.5-10 %, preferably 1.5-6 %. Prepolymers (a) have an Mn of usually 1,000-20,000, preferably 1,300-10,000, particularly 1,500- 6 , 000 .

Prepolymers (a) preferably have an HLB of 2-6.5, particularly 4-5.8, in view of dispersion stability of an aqueous dispersion of (A) and low temperature stability of a treatment. In the context of this invention, HLB is defined as Oda's HLB, determined based on conceptional diagram of organic compounds, according to Dr. Ryohei Oda , as described in "Synthesis of Surfactants and Applications thereof" (published 1957, by Maki-shoten) , page 501. (b) Bisulfite

Suitable bisulfites (b) include, for example, alkali metal bisulfites, such as sodium bisulfite and potassium bisulfite, and ammonium bisulfite, as well as mixtures of two or more of them. Among these, preferred is sodium bisulfite with respect to reactivity with (a) .

It is preferred to use (b) in the form of an aqueous solution.

Preparation of Blocked Polyurethane (A)

Preparation methods of blocked polyurethanes (A) are not particularly restricted. Synthesis of (A) can be achieved by blocking reaction of (a) with (b) , within an aqueous medium (c) , in the presence of a dispersing agent (d) .

Equivalent ratio of (b) to (a) is preferably 0.9- 1.3, particularly 0.95-1.25, in view of sufficient blocking to provide increased water-dispersibility , without resulting in reduction of water-resistance caused by residual (b) after treating textiles.

Suitable aqueous medium (c) used in blocking reaction include water and mixtures of water with a hydrophilic solvent. Suitable hydrophilic solvents include ones having a VIS of larger than 2 g/lOOg water at 25^CC , for example, hydrophilic alcohols, such as lower alcohols as mentioned in (6211); esters (C2-5) , such as methyl, ethyl and prόpyl acetates; ketones (C3-5), such as acetone, methyl ethyl ketone and diethyl ketone; glycol monoalkyl ethers (C3-7), such as (poly)ether mono-ols (e.g. cellosolves) as mentioned in (a311), and the like. Use of a hydrophilic solvent makes it possible to reduce viscosity of reaction mixture and to control easily side reactions. Preferable weight ratio of water/hydrophilic solvent is 1/9-99/1.

It is preferred to use (c) , including water used for dissolving (b) , in an amount of 20-120 %, particularly 30-100 %, based on the weight of (a), to attain dispersion of (a) with (b) easily without becoming too viscous.

Dispersing agents (d) used herein include emulsifiers and dispersants; and include surfactants (dl), high MW dispersants (d2) and combination of them.

Examples of (dl) include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants, as described in U.S. Pat. Nos. 4,331,447 and 3,929,678, incorporated herein by reference. High MW dispersants (d2) include ones having an Mn of usually 3,000-1,000,000, preferably 5,000-100,000. Illustrative of (d2) are polyvinyl alcohol; starch, cellulose and derivatives of them, such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose; carboxyl-group containing (co) polymers, such as sodium polyacrylates; urethane and/or ester linkage-containing high MW dispersants, as described in JP-A-H07-133423 and JP-A-H08-120041 , such as ones obtainable by coupling a polyester polyol (e.g. polycaprolactone polyol) and a polyether diol (e.g. PEG) with a polyisocyanate (e.g. IPDI and HDI) .

Preferably (d) has an HLB of 11-16, particularly 12-15.

Among these, preferred are nonionic surfactants, in view of dispersion stability even at coexistence with (b) . Among nonionic surfactants, preferred are 1) AO (C2- 4) 2-50 moles adducts of an aliphatic alcohol (C6-20), 2) AO (C2-4) 2-50 moles adducts or PAG esters of a fatty acid (C10-20), 3) AO (C2-4) 2-50 moles adducts of a styrenated (1-20 moles) phenols and 4) polyoxyethylene-polyoxy- propylene polyols (such as nonionic surfactants of Pluronic type and Tetronic type) , and combinations of two or more of them. More preferred are 1) and especially 3) .

It is preferred that (d) is used in an amount of 1- 10 , particularly 3-8 %, based on the weight of (a), to attain dispersion of (a) with (b) easily without reducing shrink-resistance of textiles.

In blocking reaction, addition orders of components are not particularly restricted, as far as (a) is reacted with (b) . It is preferred to add (b) into (a) , though it is also possible to add (a) into (b) . For instance, components can be added in order of 1) (a), (d) ,

(b) and then (c) ; 2) (a), (b) , (d) and then (c) ; and 3)

(c) , (d) , (a) and then (b) . Among these, preferred is 1). In case of adding a dispersing agent having hydroxyl group prior to (b) , it is preferred to add (b) imediately after adding (d) in order to suppress side reaction.

Blocking reaction is carried out at a temperature of preferably 10-60°C , more preferably 20-40°C . End point of the reaction can be confirmed by titrating unreacted (b) in the reaction product with an aqueous solution of potassium hydroxide to determine (b) content reaching equilibrium.

Blocked polyurethanes (A) thus obtained contain a blocked isocyanate group (-NHCO-SO3M; M is alkali metal or ammonium cation) preferably in an amount of 1-25 %, particularly 3-15 % .

Treatment Composition

Treatment of the present invention comprises an aqueous dispersion of a blocked polyurethane (A) and a hydrophobic solvent (B) and/or an electrolyte (C) , dispersed within an aqueous dispersion medium. Suitable aqueous dispersion medium include water and mixtures of water with a hydrophilic solvent. Suitable hydrophilic solvents include the same ones as in (c) . Weight ratio of water/hydrophilic solvent in the aqueous dispersion medium is preferably 100/0-80/20, more preferably 100/0-90/10.

In an aspect of the present invention, (B) is preferably contained in an amount of 2-30 %, more preferably 3-25 %, particularly 5-20 %, based on the weight of (A) , to attain improved low temperature stability without leaving soluble components and exhibit migration resistant properties, without lowering dispers- ibility of aqueous dispersions.

The presence of (B) makes it possible to reduce solubility of (A) in aqueous medium. For instance, solubility of (A) in aqueous medium, which is generally 20- 100 g/lOOg aqueous medium at 25°C without (B) , can be reduced to 1-10 g/lOOg aqueous medium at 25°C upon addition of (B) .

In another aspect of this invention, (C) is preferably contained in an amount of 0.5-5 %, more preferably 1-3 % , based on the weight of (A), to exhibit improved migration resistant properties, without causing deposition of polyurethanes within treatments or on squeeze rolls such as mangles .

Preparation of treatments of the invention can be accomplished, for example, by a method adding (B) and/or (C) and optionally an additional aqueous medium (D) to (A) to disperse and dilute them. Aqueous medium (D) added additionally is preferably water, but there may also be used a mixture of water with a hydrophilic solvent as mentioned in (c) . Preferable weight ratio of water/hydro- philic solvent in (D) is 100/0-90/10. In this method, addition orders of (B) and/or (C) and (D) are not particularly restricted. (D) may be added prior to (B) and/or (C) , after (B) and/or (C) , or intermediate stage between (B) and (C) . It is preferred to add (B) and (D) to (A) followed by adding (C) .

In another method, (B) may be added before or during brocking reaction to prepare a dispersion of (A) containing (B) , optionally followed by adding thereto (C) and/or (D) .

Treatments of this invention may further contain a dibasic acid dihydrazide (E) . Suitable dibasic acids constituting (E) include carbonic acid and dicarboxylic acids, such as those mentioned among (i3). Exemplary of (E) are carbodihydrazide, hydrazides of aliphatic dicarboxylic acid (C2-40), such as glutaric hydrazide and adipic hydrazide (hereinafter referred to as GD and AD, respectively) , and hydrazides of aromatic dicarboxylic acids, such as isophthalic hydrazide and terephthalic hydrazide. Among these, preferred are aliphatic dicarboxylic acid hydrazides, in view of feelings of treated fabrics. It is preferred in view of imparting better water- resistance of treated textile materials even with softer feelings to use (E) in such an equivalent ratio of hydrazide group to blocked isocyanate group of (A) in the range of 0.1-0.7, particularly 0.2-0.5. (E) is preferably added after adding (A) , (B) , (C) and (D) .

Treatments according to the present invention, may optionally contain one or more additives, for example, defoamers (such as silicone defoamers and hydrophobic polyether defoamers) , wetting agents ( surfactants having an HLB of 12-18, such as EO adducts of higher fatty alcohol (C6-20)] .

Illustrative composition of suitable treatments are as follows: usually preferably

Blocked polyurethane (A) 10-50 % 15-45 %

Hydrophobic solvent (B) 0-15 % 0.3-13 %

Electrolyte (C) 0-2.5 % 0.1-1.5 %

Total of [(B)+(C)] 0.1-17.5 % 0.4-14.5 %

Dibasic acid dihydrazide (E) 0-8 % 0.1-5 % Total of [ (A)+(6)+(C)+(E) 1 11-65 % 16-55 % Dispersing agent (d) 0-5 % 0.1-4 %

Additive (defoamer, etc.) 0-1 % 0.1-0.5 %

Solid content 10-70 % 15-60 %

Aqueous medium [(c)+(D)] 30-90 % 40-85 %

In the above and hereinafter, solid content is content of evaporation residue after drying for 45 minutes at 130°C . There may be added a pH adjustor to provide a treatment having a pH of 6-9. Illustrative of pH adjustors are alkaline materials, for example, strong base salts (such as alkalimetal salts) of a weak acid having a pKa of more than 2 (such as carbonic and phosphoric acids), such as sodium bicarbonate; and acidic metarials such as carbonic acid.

Treatment of the invention may be used in combination with another treatment, which may be applied to textile materials either separately or admixed with the treatment of the invention. Suitable other treatments include, for example, various resin emulsions, such as emulsions of polyurethane other than (A) , acrylic emulsions and SHR latices; textile softeners, such as silicone type softeners (e.g. amino-containing silicone emulsions); and combinations of two or more. When used admixed with the treatment of the invention, said another treatment is preferably used in such an amount of not more than 100 %, particularly not more than 70 %, based on the solid content of the treatment of the invention.

Application of Treatment

Treatments of the present invention can be applied to textile materials of. various fibres, for example, natural fibres, such as wool, cotton and silk; regenerated fibres, such as rayon and acetate; and synthetic fibres, such as polyester, polyamide and polyacrylonitrile . Suitable textile materials include textiles, such as knitts and woven fabrics, and nonwoven fabrics. Treatments of this invention are particularly useful for finishing fabrics of natural fibres (especially wool) to impart soft feelings and shrink-resistance .

Treatments of the invention can be applied onto textiles as follows: 1) diluting a treatment with water to prepare a dilute treatment liquor; 2) applying the treatment liquor onto a textile; 3) squeezing the textile with a mangle or the like to a desired pickup; and 4) predrying and then heat-treating the textile.

Dilute treatment liquors generally have a solid content of 1-5 %. Suitable applying means of treatment liquors include, for example, roll coating, dipping and spraying. Pickup of treatment liquors is usually 2-100 g/ 100 g of textile. Predrying and heat-treating can be carried out, for instance, under conditions of 2-5 minutes at 80-130°C and 1-3 minutes at 130-170°C , respectively.

Total pickup (solid content after heat-treating) of [ (A) + (C) + (E) ) contained in treatment onto textile is usually 0.5-5 %, preferably 0.8-4.5 %, based on the weight of the textile before treating.

In case of applying another treatment to textile separately . or admixed with the. treatment of the invention, total pickup (solid content after heat-treating) of said another treatment and the treatment of the invention onto textile is usually 0.5-10 %, preferably 0.8-9 %, based on the weight of the textile before treating.

[Examplesl

Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and not intended to be limiting unless otherwise specified. Production Example 1

Into a reaction vessel equipped with a thermometer and a stirrer, 147.5 parts of PBD (EW=1,000, F=2) and then

24.8 parts of HDI (NCO/OH=2.0) were charged, and reacted within an atmosphere of nitrogen under stirring for 6 hours at 105^CC to prepare a prepolymer (a-1) (NCO%=3.6%, HLB=2.2). Prepolymer (a-1) was cooled down to 30°C , and were added thereto under stirring 13 parts of a nonionic surfactant (d-1) ( EO (19 moles) - PO (1.5 moles) block adducts of styrenated (2.75 moles) phenol; HLB=13.8)] ,

13.9 prts of sodium bisulfate dissolved in 32.4 parts of water and 74.7 parts of ethanol, followed by continuing stirring for 90°C at 30°C to prepare a blocked polyurethane (Al).

Production Example 2

Production Example 1 was repeated except substituting 59 parts of PBD and 88.5 parts of a glycerol PO adduct (EW=1,000, F=3) for 147.5 parts of PBD to prepare a prepolymer (a-2) (NCO%=3.7%, HLB=3.8) and a blocked polyurethane (A2). Production Example 3

Production Example 2 was repeated except substituting 59 parts of PTMG (EW=1,000, F=2) for 59 parts of PBD to prepare a prepolymer (a-3) (NCO%=3.8%, HLH=5.7) and a blocked polyurethane (A3). Examples 1-4 and 7

Treatments were prepared, in accordance with the formulation written in Table 1, by admixing 23.4 parts of a solvent with 306.3 parts of (A), followed by adding thereto 776.3 parts of water and a salt written in Table 1 and mixing them for 30 minutes to form aqueous dispersions . Example 5

Example 3 was repeated except substituting 1-HP for MIBK and using no salt. Example 6

Example 3 was repeated without using any solvent. Examples 8-12

Treatments were prepared in accordance with the formulation written in Table 1, by further admixing the aqueous dispersions prepared in Examples 1-5 with (D) written in Table 1. Comparative Example 1

Example 6 was repeated except using no salt. Comparative Example 2

Example 5 was repeated except using substituting DEK (diethyl ketone: WS=3.4) for 1-HP. Comparative Examples 3 and 4

Examples 6 and 10 were repeated except substituting NaAc (sodium acetate: salt of acetic acid having a pKa of 4.56) for Na₂S0₄. Table 1

Treatments thus prepared were evaluated by the following test methods. The results are shown in Table 2 Table 2

Test Method 1 (Settling Stability)

Each treatment is allowed to stand at 10°C , and is measured how many days will it take until settlings become observed with eyes. Test Method 2 (Flexural Rigidity of Treated Textile)

1) Dilute treatment liquor is prepared by mixing 100 parts of each treatment, 20parts of a penetrant [ EO 9 moles adduct of sec-alcohol (C12-14)] , 1 part of sodium hydrogen carbonate and 847 parts of water.

2) Undyed wool serge (size: 25 cm X 25 cm) for testing is dipped into the treatment liquor, and adjusted with a mangle to squeeze ratio of 60 %, followed by drying and heat-treating the dipped textile for 5 minutes at 130^CC to obtain a treated textile. Each treated textile is cut into a size of 20 cm x 20 cm and is allowed to stand for 3 hours under conditions of 50 % R.H. at 25°C , followed by measuring flexural rigidity of treated textile with a KES sheer bending tester.

Test Method 3 (Area Shrink after Detergent Washing of Treated Textile)

Each treated textile cut into a size of 20 cm x 20 cm prepared as in Test Method 2 is washed under the following conditions to measure area retraction.

In accordance with JIS L-1027, Method 103, using a household washing machine, cycles of washing for 5 minutes with warm water at 40°C containing 2g/L of a detergent at a liquor ratio of 1/60, rinsing for 2 minutes and dehydrating followed by horizontal drying are repeated 20 times, 40 times and 60 times. Area retraction (AR, %) after washing is determined according to the following equation:

AR=(LoX Wo — LX W)X 100/(L_oX Wo) wherein Lo represents distance between two gage marks of lengthwise direction before washing, Wo represents distance between two gage marks of width direction before washing, L represents distance between two gage marks of lengthwise direction after washing, and W represents distance between two gage marks of width direction after washing .

INDUSTRIAL APPLICABILITY

Treatments of the present invention containing (B) are stable even at a lower temperature, without forming deposits .

Treatments of this invention containing (C) are capable of preventing or reducing migration of resins on finished textile products and providing textile products of soft feelings together with improved shrink-resistance.

Thus, treatments of the invention are useful for finishing textile products, such as knitts, woven fabrics and nonwoven fabrics, of natural, regenerated and synthetic fibres.

Claims

1. A textile treating composition, which comprises an aqueous dispersion containing:

(A) a blocked polyurethane of an NCO-terminated urethane prepolymer (a) blocked with a bisulfite (b) , and (6) a hydrophobic solvent having a water-solubility of at most 2g/100g water at 25°C , and/or

(C) an electrolyte comprising a salt of a strong acid having a pKa of not more than 2, and having a molar conductance (Λ ), of 0.01 mole % aqueous solution at 25°C , in the range of 110-130 S* cm²/mole, dispersed within an aqueous dispersion medium.

2. The composition of Claim 1, wherein (a) has an HL6 of 2-6.5.

3. The composition of Claim 1 or 2, which contains (6) in an amount of 2-30 % by weight based on the weight of (A) .

4. The composition of Claim 1, 2 or 3 , wherein (B) is at least one selected from the group consisting of hydrophobic alcohols (Bl), esters (B2), ethers (B3), ketones (B4), hydrocarbons (B5) and halogenated hydrocarbons (B6); preferably selected from the group consisting of (Bl), (B2), (B3) and (B4), particularly aliphatic monohydric alcohols, aliphatic carboxylic acid alkyl esters, glycol monoalkyl ethers and dialkyl ketones.

5. The composition of any one of Claims 1-4, wherein said salt of (C) is at least one selected from the group consisting of metallic salts, ammonium salts and salts of organic bases; preferably selected from the group consisting of salts of alkali metals, alkaline earth metals, copper, silver and zinc.

6. The composition of any one of Claims 1-5, which contains (C) in an amount of 0.5-5 % by weight based on the weight of (A) .

7. The composition of any one of Claims 1-6, wherein (A) is obtainable by blocking reaction of (a) with (b) , within an aqueous medium (c) , in the presence of a dispersing agent (d) , preferably selected from the group consisting of surfactants (dl) and high molecular weight dispersants (d2) .

8. The composition of any one of Claims 1-7, which is obtainable by adding (B) and/or (C) and optionally an additional aqueous medium (D) to (A) .

9. The composition of any one of Claims 1-8, which further comprises a dibasic acid dihydrazide (E) .

10. The composition of any one of Claims 1-9, which comprises 10-50 % by weight of (A) , 0-15 % by weight of (B) , 0-2.5 % by weight of (C) , 0-8 % by weight of a dibasic acid dihydrazide (E) , 0.1-5 % by weight of dispersing agent (d) , 0-1 % by weight of another additive and 30-90 % by weight of aqueous medium.

11. A method for treating a textile, which comprises ^aPPlying a composition according to any one of Claims 1-10 onto a textile material.

12. A method for treating a textile, which comprises heat-treating a textile material treated with a composition according to any one of Claims 1-10.

13. The method of Claim 11 or 12, wherein the textile material is selected from the group consisting of knitts, woven fabrics and nonwoven fabrics; preferably a wool textile .

14. A textile product obtainable by the method of Claim 11, 12 or 13.