JP2003129382A - Fiber treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fiber treating agent comprising a blocked polyurethane- based aqueous dispersion stable even at a low temperature, to provide a method for processing a fiber and to obtain a fiber product. SOLUTION: This fiber treating agent comprises the aqueous dispersion containing the blocked polyurethane (A) which is obtained by blocking an isocyanate terminated urethane prepolymer (a) with a hydrogensulfite (b) and a hydrophobic solvent (B) having <=2 g/100 g water) solubility at 25 deg.C. This method for processing a fiber comprises using the fiber treating agent. This fiber product is obtained by processing with the fiber treating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fiber treatment agent. More specifically, the present invention relates to a fiber treatment agent used for finishing a fiber product such as a knitted fabric, a woven fabric, and a nonwoven fabric.

[0002]

2. Description of the Related Art Heretofore, as a fiber treating agent, a fiber treating agent comprising an aqueous dispersion obtained by blocking a urethane prepolymer with a bisulfite has been known. (For example, JP 2000
-265374). However, the fiber treating agents composed of these aqueous dispersions have a problem that, since a large amount of blocked polyurethane is dissolved in an aqueous medium, they are precipitated and settled especially at a low temperature (for example, 10 ° C. or lower). There was a point.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber treatment agent comprising a blocked polyurethane-based aqueous dispersion which is stable even at a low temperature.

[0004]

Means for Solving the Problems The present inventors have intensively studied a fiber treating agent which is stable even at a low temperature and does not generate precipitates, and as a result, has reached the present invention. That is, the present invention relates to a blocked polyurethane (A) obtained by blocking an isocyanate-terminated urethane prepolymer (a) with a bisulfite (b), and a solubility (g / 100 g) of 2 or less at 25 ° C.
A fiber treatment agent comprising a water-based aqueous dispersion containing a hydrophobic solvent (B), a method for processing fibers with the fiber treatment agent, and a fiber product processed with the fiber treatment agent.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The hydrophobic solvent (B) has a solubility in water of 2 or less, preferably 1.8 or less (g / 100 g).
Water, 25 ° C .: hereinafter abbreviated as WS).

(B) includes, for example, hydrophobic alcohols (B1), esters (B2), ethers (B3),
Ketones (B4), hydrocarbons (B5), halogenated hydrocarbons (B6) and combinations of two or more of these.

(B1) preferably has 6 to 1 carbon atoms.
8, more preferably 6 to 12, particularly preferably 6 to 9.
Contains alcohol.

The following is an example of (B1). (B11) Examples of the monohydric alcohol include aliphatic saturated monohydric alcohols, aliphatic unsaturated alcohols, alicyclic alcohols, and aromatic alcohols.

The aliphatic saturated monohydric alcohols include straight-chain and branched alkanols such as, for example, natural alcohols and synthetic alcohols (eg, Ziegler alcohol or oxo alcohol), and specifically 2-ethylbutanol, 2 and 4-alkanol. Methylpentanol, 1-hexanol, 2-ethylpentanol, 2-methylhexanol, 1-, 2- and 3-heptanol, 2-ethylhexanol, 1 and 2-octanol, 1-nonanol, decanol, undecanol, dodecanol and And tridecanol.

The aliphatic unsaturated alcohols include, for example, alkenols and alkadienols, and specifically include 2-propylallyl alcohol, 2-methyl-4-pentenol, 1-hexenol, 2-ethyl-4-enol. Examples include pentenol, 2-methyl-5-hexenol, 1-heptenol, 2-ethyl-5-hexenol, 1-octenol, 1-nonenol, undecenol, dodecenol, geraniol, and the like.

The alicyclic alcohols include, for example, cycloalkanols and cycloalkenols, and specific examples include methylcyclohexanol and α-terpineol.

Examples of the aromatic alcohol include phenethyl alcohol and salicyl alcohol.

(B12) As the dihydric alcohol, an alkanediol such as 1,6-hexanediol,
Examples include 1,8-octanediol and 1,12-dodecanediol.

Among (B1), preferred are (B11) and more preferred are aliphatic alcohols from the viewpoint of emulsification and dispersibility in an aqueous dispersion.

(B2) includes a hydrocarbyl ester (B21) having a total carbon number of 4 to 24, preferably 6 to 18, and more preferably 6 to 12, and a total carbon number of 4 to 60;
Preferably 6 to 30, more preferably 6 to 24 polyol esters (B22) are included.

Hydrocarbyl esters (B21) include hydrocarbyl carboxylate esters such as hydrocarbyl monocarboxylic acid (B211) and mono-carboxylates.
And di-hydrocarbyl dicarboxylic acid (B212)
Is included. Above and below, a hydrocarbyl group refers to a monovalent hydrocarbon group, for example, a (cyclo) aliphatic hydrocarbon group such as a (cyclo) alkyl and (cyclo) alkenyl group, and a (alkyl) aryl and aralkyl group. Means an aromatic hydrocarbon group. Also,
(Cyclo) aliphatic represents an aliphatic and / or alicyclic group, and the same expression is used hereinafter.

The monocarboxylic acids constituting (B211) include straight-chain and branched, and saturated and unsaturated carboxylic acids (fatty acids) having 2 to 20 carbon atoms, and specifically include acetic acid and propionic acid. , Butyric acid, isobutyric acid, octanoic acid,
Examples include 2-ethylhexanoic acid, lauric acid, palmitic acid, myristic acid, stearic acid, abietic acid, (meth) acrylic acid, (iso) crotonic acid, oleic acid and tall oil fatty acid.

(B211) includes hydrocarbyl esters of the above-mentioned monocarboxylic acids [(B11) or esters with lower alcohols having 1 to 5 carbon atoms (alkanols or alkenols)], such as n-butyl acetate, Isoamyl acetate, hexyl acetate, octyl acetate,
Acetates such as dodecyl acetate, octadecyl acetate, vinyl acetate, octenyl acetate and dodecenyl acetate, the corresponding propionates (such as butyl propionate and hexyl propionate), butyrate esters (such as hexyl butyrate), and isobutyrate esters (such as hexyl isobutyrate) Such)
And stearic acid esters (such as butyl stearate), and (meth) acrylic acid esters (such as methyl methacrylate and butyl methacrylate).

The dicarboxylic acids constituting (B212) include saturated or unsaturated dicarboxylic acids having 4 to 8 carbon atoms (succinic acid, glutaric acid, adipic acid, ethylsuccinic acid, pimelic acid, maleic acid, fumaric acid and itaconic acid). Acids, etc.).

As (B212), mono- and dihydrocarbyl esters of the above dicarboxylic acids [(B1
1) or esters of the above lower alcohols (alkanols or alkenols)], for example, mono- and dialkyl succinates (mono- and di-2-succinates)
Ethylhexyl, mono- and didodecyl succinate, dimethyl succinate and diethyl succinate, etc., mono- and dialkyl glutarates (such as dimethyl glutarate) and mono- and di-alkyl adipates (such as mono- and dimethyl adipate).

The polyol constituting (B22) includes a diol and a polyol having 3 to 8 or more hydroxyl groups, and the diol has 2 to 12 carbon atoms.
(Cyclo) alkanediol [ethylene glycol (hereinafter abbreviated as EG), propylene glycol, 1,
2-, 2,3-, 1,3- and 1,4-butylene glycol (hereinafter abbreviated as BG), neopentyl glycol (hereinafter abbreviated as NPG), 1,6-hexylene glycol (hereinafter abbreviated as HG) ), Cyclohexanediol, cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol (hereinafter abbreviated as TMPG) and the alkanediol shown in (B12), and aromatic diols such as xylene diol ]. Examples of the polyol having three or more hydroxyl groups include alkane polyols and their intramolecular and intermolecular dehydrates [glycerin, trimethylolpropane (hereinafter abbreviated as TMP), pentaerythritol, sorbitol, polyglycerin, dipentane Erythritol and sorbitan] and sucrose and glycosides [such as sucrose and methylglucoside].

(B22) includes mono- and polyesters of polyol and monocarboxylic acid, for example, HG mono- and diacetate, EG mono- and di-2-ethylhexanoate, NPG mono- and di-2-ethylhexanoate , NPG mono and diisobutyrate, TMPG mono and di-2-ethylhexanoate, TMPG mono and diisobutyrate, TMP mono, di and tri-2-ethylhexanoate, sorbitan mono, di and tri fatty acids (carbon number 12-1
8) Esters (having an HLB of 1 to 7 according to the Oda method described later) and the like.

Preferred among (B2) are polyol esters (B22), more preferably mono- and diesters of polyols and monocarboxylic acids, particularly preferably diols, from the viewpoint of emulsification and dispersibility in aqueous dispersions. Monoesters with monocarboxylic acids, especially NPG
Mono 2-ethylhexanoate, NPG monoisobutyrate, TMPG mono 2-ethylhexanoate, TMPG monoisobutyrate (TMPG monoisobutyrate will be abbreviated as TMIE hereinafter), and a combination of two or more thereof It is.

(B3) includes a hydrocarbyl ether (B31) having 5 to 18, preferably 6 to 12, more preferably 6 to 8 carbon atoms and having one or two ether bonds, and 2 to 60 carbon atoms. And a polyalkylene ether (B32) having a number average molecular weight of 3,000 or more (measured by gel permeation chromatography; hereinafter abbreviated as Mn).

As (B31), dihydrocarbyl ether (B311) [for example, methyl n-pentyl ether, methyl n-octyl ether, isopropyl n
-Butyl ether, ethyl n-hexyl ether, di-n
-Butyl ether and isobutyl 2-ethylhexyl ether, etc.] and mono- and polyhydrocarbyl ethers of polyols (B312) [polyols include those mentioned above in (B22)] [eg EG mono and di-2- Ethylhexyl ether, E
G mono and didecyl ether, BG mono and di 2-
Ethylhexyl ether, HG mono and diisobutyl ether, HG mono and dipentyl ether, and TMP mono, di and tri 2-ethylhexyl ether, etc.].

The polyalkylene ether (B32) includes
Polyoxyalkylene polyol having an oxyalkylene group having 3 to 12 carbon atoms (B321);
Hydrocarbyl ethers of polyoxyalkylene polyols having an oxyalkylene group (B322); and esters of the polyoxyalkylene polyols having an oxyalkylene group having 2 to 12 carbon atoms with the monocarboxylic acids mentioned in the above (B21) Or, a part thereof is hydrocarbyl ether (B323).

The above-mentioned polyoxyalkylene polyols include polyalkylene glycols and alkylene oxide (hereinafter abbreviated as AO) adducts of polyols. The polyols include those similar to those shown in (B22). As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- and 1,
3-butylene oxide, tetrahydrofuran (hereinafter, referred to as
THF), α-olefin oxides having 5 to 12 carbon atoms, and combinations of two or more of these (block and / or random addition).

Examples of (B321) include polyalkylene glycol [polypropylene glycol (Mn = 80)
0-3,000), polytetramethylene ether glycol (hereinafter abbreviated as PTMG) (Mn = 300-7)
00), PO and THF block and random copolymers (Mn = 500 to 1,000), and polyoxypropylene triol (Mn = 800 to 3,000)
[Glycerin PO adduct and TMP PO adduct and the like].

Examples of (B322) include mono- and di-alkyls of the above-mentioned polyalkylene glycols (C1
4) ethers, AO adducts of the monohydric alcohols mentioned in (B11) (AO as EO, PO and / or T
HF), dimers of these monoethers and / or AO adducts (dimerization by using alkylene dihalides such as methylene dichloride), mono-, di- and trialkyls of the above polyoxypropylene triols (carbon number 1-4) ethers, and mono- and dialkyl (C 1-4) ethers of polyethylene glycol (Mn = 106-370) [aliphatic alcohols having an HLB of 1-7 according to the Oda method described below (C 10-2)
4) EO (2-8 mol) adducts, such as di-2-ethylhexyl ether of diethylene glycol and distearyl ether of triethylene glycol].

Examples of (B323) include mono- and diacetates of the above-mentioned polyalkylene glycols, mono-, di- and tri-acetates of the above-mentioned polyoxypropylene triols, and mono- and di-alkyls of the above-mentioned polyoxypropylene triols. Monoacetates of ethers; 2 corresponding to these acetates
-Ethylhexanoate; and diesters of polyethylene glycol (Mn = 106 to 300) and monocarboxylic acid (C8 to C18) [eg, diethylene glycol di-2-ethylhexanoate and triethylene glycol distearate] Is mentioned.

Among (B3), preferred are (B31), more preferred (B312), and particularly preferred are glycol monoalkyl ethers from the viewpoint of emulsifying dispersibility in an aqueous dispersion.

(B4) includes ketones having a total carbon number of 4 to 24, preferably 6 to 12, and more preferably 6 to 8. As (B4), for example, dihydrocarbyl ketone [for example, methyl isobutyl ketone (hereinafter, MIBK)
Abbreviations), aliphatic dihydrocarbyls such as diisopropyl ketone, methyl amyl ketone, ethyl isobutyl ketone, diisobutyl ketone, isobutyl isoamyl ketone, diisoamyl ketone, isobutyl allyl ketone, isopropyl allyl ketone, ethyl octenyl ketone and diallyl ketone ( Alkyl and / or alkenyl) ketones] and cyclic ketones such as cyclohexanone. Of these, preferred are aliphatic ketones, and more preferred are dialkyl ketones, especially MIBK.

(B5) contains a hydrocarbon having 4 to 24, preferably 6 to 12, and more preferably 6 to 8 carbon atoms. Examples of (B5) include (cyclo) aliphatic hydrocarbon (B51) [linear and branched alkanes (such as n-hexane, n-octane, n-nonane, n-decane, isooctane and isodecane); -Octene, 2-octene, 1-nonene, 1-decene and 1-
Cycloalkanes (such as cyclohexane, cyclodecane, cyclododecane, cyclohexene and cyclododecene); and cycloalkenes (such as cyclohexene and cyclodecene)]; and aromatic hydrocarbons (B52) [toluene, xylene, cumene, ethylbenzene and styrene and the like] ]. Of these, preferred are (cyclo) aliphatic hydrocarbons (B5
1).

(B6) includes halogenated hydrocarbons having 4 to 24, preferably 6 to 12, more preferably 6 to 8 carbon atoms and containing 1 to 4 halogen atoms (chlorine, bromine and iodine). Is included. Examples of (B6) include aliphatic halogenated hydrocarbon (B61) [dichloromethane,
Chloroform, carbon tetrachloride, dichloroethane, trichloroethane and dichloropropane etc.] and halogenated aromatic hydrocarbons (B62) [chlorobenzene, bromobenzene, dichlorobenzene and benzyl chloride etc.]
Is mentioned.

Among these solvents (B), preferred are (B1), (B2), (B3) and (B4), and more preferred are (B1), (B2) and (B3). Particularly preferred is (B2).

(B) is preferably liquid at normal temperature from the viewpoint of easy handling. Further, the boiling point (under normal pressure) of (B) is preferably 300 ° C. or lower, more preferably 2 in terms of being easily evaporated and removed from the treated textile.
50 ° C. or less.

(B) shows the solubility (g / 100) of (A) in an aqueous medium in an aqueous dispersion containing (A).
g Aqueous medium, 25 ° C .; hereinafter abbreviated as AMS). For example, AMS 20 ~
By adding (B) to the aqueous dispersion containing 100 (A), an aqueous dispersion having AMS reduced to 1 to 10 can be obtained.

In the present invention, the blocked polyurethane (A) is obtained by blocking an isocyanate-terminated prepolymer (a) with a bisulfite (b), and comprises an isocyanate-terminated prepolymer (a) [hereinafter, a prepolymer (A) a) is derived from an organic polyisocyanate (a1) and an active hydrogen atom-containing compound such as a polyol.

(A1) includes diisocyanate and 3
Functional or higher polyfunctional isocyanates included;
For example, carbon number (excluding carbon in NCO group, the same applies hereinafter)
6-20 aromatic polyisocyanate, 2-18 carbon atoms
Aliphatic polyisocyanate, alicyclic polyisocyanate having 6 to 15 carbon atoms, araliphatic polyisocyanate having 8 to 15 carbon atoms, and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, buret group Uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) and mixtures of two or more of these.

As the aromatic polyisocyanate (a11), for example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-
Tolylene diisocyanate (TDI), crude TDI,
2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3 '-Dimethyl-4,4'-
Diisocyanatodiphenylmethane, crude MDI, 1,5
-Naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, and m- and p-isocyanatophenylsulfonyl isocyanate.

Examples of the aliphatic polyisocyanate (a12) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate,
6,11-undecane triisocyanate, 2,2,4
-Trimethylhexamethylene diisocyanate, lysine diisocyanate (2,6-diisocyanatomethylcaproate), bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2, 6-diisocyanatohexanoate and the like.

As the alicyclic polyisocyanate (a13), for example, isophorone diisocyanate (IPD
I), hydrogenated MDI, cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-
1,2-dicarboxylate, and 2,5- and / or
Or 2,6-norbornane diisocyanate.

Araliphatic polyisocyanate (a14)
Examples thereof include m- and / or p-xylylene diisocyanate, and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Further, a modified polyisocyanate (a1
Examples of 5) include (a11) to (a14) such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, buret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. And mixtures of two or more of these (for example, a combination of modified MDI and urethane-modified TDI (isocyanate group-containing prepolymer)).

Among (a11) to (a15), a non-aromatic polyisocyanate is preferable in that the treated fiber does not discolor, and (a12) is more preferable in terms of the texture of the treated fabric. (A preferable polyisocyanate is diisocyanate.)

The active hydrogen atom-containing compound constituting the prepolymer (a) includes the polyol (a2).
(A2) includes a polymer polyol (a21), and the hydroxyl equivalent (a21) of the hydroxyl equivalent (number average molecular weight per hydroxyl group; a value calculated from the hydroxyl value: hereinafter abbreviated as EW) is at least 400, preferably Is 500 to 2,000
0, more preferably 600 to 1,700.

Examples of (a21) include polyether polyol (a211) and polyester polyol (a
212) and a hydroxyl-containing vinyl polymer (a213).

The polyol (a2) has an EW of less than 400
A low molecular weight polyol (a22) having (calculated from the hydroxyl value) is added to (a21) or (a2)
It may be contained instead of 1).

The polyether polyol (a211) is
It has a structure obtained by adding one or more AO to an initiator (i) having at least two (preferably 2 to 8) active hydrogen atoms.

AO includes those having 2 to 12 or more carbon atoms as described above. Preferred among the AOs are PO and a combination of PO and another AO (for example, EO). Further, it is preferable that 30% or more of the total amount of AO is PO.

The initiator (i) contains a polyhydric alcohol (i1), a polyhydric phenol (i2), a (hydroxy) carboxylic acid (i3), an amine (i4), a polythiol (i5) and a phosphorus atom. Acid (i6) is included, and specific examples thereof include the following.

(I1) Polyhydric alcohol; (b2)
The diols mentioned in 2) (eg EG and PG) and 3
And polyols having up to 8 or more hydroxyl groups (such as TMP). (I2) Polyhydric phenols; monocyclic polyvalent (2- to 4-valent) phenols [hydroquinone, resorcin, catechol, phloroglysin, etc.], bisphenols [bisphenol A, bisphenol F, bisphenol S, US Pat. No. 4,990,545] And the like, and phenol-formaldehyde condensates (novolak and resole). (I3) (hydroxy) carboxylic acid; polycarboxylic acid having 2 to 8 or more carboxyl groups (i3
As 1), for example, an aliphatic polycarboxylic acid (having 2 carbon atoms)
~ 40) [Saturated aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, ethylsuccinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, maleic acid, fumaric acid Acids, itaconic acid, unsaturated aliphatic polycarboxylic acids such as citraconic acid and mesaconic acid, and unsaturated monocarboxylic acids or polymers of the above unsaturated dicarboxylic acids having a polymerization degree of 2 to 8 (maleic acid dimer, Dimer of itaconic acid, pentamer of acrylic acid, pentamer of methacrylic acid, etc.)], alicyclic polycarboxylic acid, for example, alicyclic dicarboxylic acid [1,2- and 1,3-cyclopentanedicarboxylic acid] Acid, 1,2-, 1,3-, 1,4-cyclohexanedicarboxylic acid, etc.], polymerized fatty acid [dimer acid and trimer acid (linolein And dimers and trimers of unsaturated fatty acids such as linoleic acid)] and aromatic polycarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, etc.]. Examples of the hydroxycarboxylic acid (i32) include compounds having one or more hydroxyl groups and one or more carboxyl groups in one molecule, for example, aliphatic hydroxy groups such as glycolic acid, lactic acid, glyceric acid, tartaric acid and ricinoleic acid. Carboxylic acids, as well as aromatic hydroxycarboxylic acids such as salicylic acid are mentioned.

(I4) amines; primary monoamines (i4
As 1), an aliphatic primary monoamine having 1 to 20 carbon atoms [monoalkylamine (methylamine, ethylamine,
Propylamine, n-butylamine, etc.) and monoalkenylamines (oleylamine, etc.)], alicyclic 1
Primary monoamines such as cyclohexylamine, and aromatic primary monoamines such as benzylamine and aniline. As the polyamine (i42), a polyamine having 2 to 10 amino groups, for example, an aliphatic polyamine [alkylenediamine (2 to 18 carbon atoms), polyalkylene (2 to 6 carbon atoms) polyamine (3 to 10 amino groups) Specifically, ethylene diamine, propylene diamine, tetramethylene diamine,
Hexamethylenediamine, diethylenetriamine, dipropylenetriamine, N-methylaminoethylamine, etc.], aromatic polyamine (C6-20) [2,
4- and 2,6-tolylenediamine, 4,4'- and 2,4'-diphenylmethanediamine, polymethylenepolyphenylenepolyamine, triphenylmethanetriamine, etc.) and their partial alkyls (C1
To 8) Substituents.

Examples of the polythiol (i5) include those having a structure in which the hydroxyl group of the polyhydric alcohol (i1) is a thiol group, and specific examples thereof include ethylenedithiol, propylenedithiol, 1,4-butanedithiol, and dodecanedithiol. Is mentioned.

As the acid (i6) containing a phosphorus atom,
Examples include phosphoric acids (phosphoric acid, pyrophosphoric acid and polyphosphoric acid), phosphorus, phosphonic acid, phosphinic acid and partial alkyl (1-8 carbon atoms) esters of these acids (such as dibutyl pyrophosphate).

Of these, preferred are polyhydric alcohols (i1) and further aliphatic polyhydric alcohols, and particularly preferred are triols and diols, especially diols.

The polyether polyol (a211) is
One or more A to the initiator (i) in the presence of a catalyst
It is obtained by ring-opening addition polymerization of O. Examples of the catalyst include an anion addition polymerization catalyst (eg, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, and cesium hydroxide), a cation addition polymerization catalyst, and a coordination anion addition polymerization catalyst. Among these, production from an anion addition polymerization catalyst is preferred from the viewpoint of economy and productivity.
Ring-opening addition polymerization is usually carried out at 40 to 150 ° C, preferably 90 to
It can be performed at a temperature of １３０130 ° C.

The polyether polyol (a211) is
Two or more AO adducts can also be obtained by performing a coupling reaction using a coupling agent such as an alkylene dihalide (e.g., having 1 to 4 carbon atoms, such as methylene dichloride).

As (a211), for example, polyethylene glycol, polypropylene glycol, PTMG
And linear polyether diols such as the EO and / or PO adducts of bisphenol A, and branched polyether polyols such as the EO and / or PO adducts of glycerin.

Examples of the polyester polyol (a212) include a condensed polyester polyol (a2121) obtained from a polyol and a polycarboxylic acid, a polylactone polyol (a2122) obtained by ring-opening polymerization of lactone in the presence of a polyol, and castor oil. And castor oil polyols (a2123) such as transesterification products of castor oil and polyol, and polycarbonate polyols (a2124) obtained by ring-opening polymerization of alkylene carbonate in the presence of polyol.

(A2121), (a2122), (a2
The polyols that can be used in (123) and (a2124) include polyhydric alcohol (i1) and polyoxyalkylene polyol [(a211) and A to initiator (i)].
Low molar number adduct of O, etc.].

The polycarboxylic acid constituting (a2121) includes the aforementioned (i31). Of these, preferred are dicarboxylic acids, especially aliphatic dicarboxylic acids such as adipic acid. Among the polyols (a2121)
Preference is given to using polyhydric alcohols, especially diols (eg, EG, DEG, BG, HG and NPG) and these in small amounts (up to 20%, preferably 1%).
0% or less) in combination with a polyol having 3 to 4 hydroxyl groups (such as TMP).

(A2121) can be produced by reacting a polyol with a polycarboxylic acid or an ester-forming derivative thereof (acid anhydride, acid halide, lower alkyl ester). It can be produced by reaction with AO.

As specific examples of (a2121), poly (ethylene adipate) diol, poly (butylene adipate) diol, poly (hexamethylene adipate)
Diols, poly (neopentyl adipate) diols,
Examples thereof include poly (ethylene / butylene adipate) diol, poly (neopentyl / hexyl adipate) diol, poly (3-methylpentyl adipate) diol, and poly (butylene isophthalate) diol.

(A2122) is obtained by ring-opening polymerization of a lactone having 4 to 13 carbon atoms (eg, ε-caprolactone, δ-valerolactone) in the presence of a polyhydric alcohol. Poly ε-caprolactone diol, poly-3-methyl δ-valerolactone diol and the like can be mentioned.

(A2123) includes castor oil, halogenated castor oil, an AO low-mol (1 to 3 mol) adduct of castor oil, and a transesterification product of the above-mentioned polyols (eg, EG, TMP, pentaerythritol) with castor oil. And so on.

The alkylene carbonate constituting (a2124) includes an alkylene carbonate having 3 to 13 carbon atoms, for example, ethylene, propylene and hexamethylene carbonate. Specific examples include polyethylene carbonate diol and polyhexamethylene carbonate diol.

Of these, preferred is (a212)
1).

Examples of the hydroxyl group-containing vinyl polymer (a213) include polyolefin polyols (a2131), for example, olefins and, if necessary, small amounts of other monomers (30% or less, preferably 15 to 20%). Polymer; and acrylic polyol (a213)
2) For example, hydroxyalkyl (2-8 carbon atoms)
(Meth) acrylates and (co) polymers of other monomers as required.

As the olefin, alkadiene (1,
3-butadiene) and an α-olefin having 8 to 18 carbon atoms. Other monomers in the case of copolymerization include aromatic hydrocarbon monomers such as styrene, unsaturated nitriles such as (meth) acrylonitrile,
And alkyl (C1-20) (meth) acrylate such as methyl (meth) acrylate.

As specific examples of (a2131) and (a2132), polybutadiene polyol (hereinafter referred to as PBD)
Abbreviated), halogenated PBD, α having 8 to 18 carbon atoms
Polyolefin polyol derived from olefin, hydrogenated PBD in which hydrogen is added to unsaturated double bond of PBD, hydroxyethyl (meth) acrylate and / or copolymer of methyl (meth) acrylate and styrene, and Acrylic polyol and the like can be mentioned.

Of these polyols (a2131) and (a2132), (a2131) is preferred in view of the feel of the treated fiber product.

The polymer polyol (a21) may be a vinyl-modified one, that is, a polymer polyol. The polymer polyol is (a21) [(a211)
And / or (a212) etc.] and, if necessary, a vinyl monomer in the presence of (a22). Examples of the vinyl monomer include an aromatic hydrocarbon-based vinyl monomer such as styrene, and an unsaturated nitrile such as (meth) acrylonitrile. The polymer content in the polymer polyol can vary widely, for example from 1 to 80%, preferably from 10 to 70%.

Polymer polyols (a211), (a21)
2) and (a213) can be used alone or as a mixture of two or more.

The polymer polyol (a211) has an average number of functional groups (average number of hydroxyl groups) determined by H 1 -NMR from the viewpoint of feel (not too soft and not too hard) of the treated fiber product. F), but usually 1.8 to 8 or more, preferably 2 to 4, more preferably 2.3 to 3, and particularly preferably 2.4 to 2.
9

The low molecular polyol (a22) includes
The polyhydric alcohol (diol and polyol having 3 to 8 hydroxyl groups) described in (B22), and the low molar AO adduct of (i) (with an EW of 400 or less)
And the like. Usually, (a22) has an F of 2 to 8, preferably 2 to 3. As a specific example of (a22),
EG, PG, 1,4-BG, TMP, bishydroxyalkylated dihydric phenol (for example, an adduct of bisphenol A with 2 moles of EO), bishydroxyalkylmonoihydrocarbylamine (for example, bishydroxyethylaniline) and tetrakishydroxyalkyl Diamines (e.g., tetrakishydroxypropylethylenediamine); and their low moles (1-8 x F mole) A
O adduct and the like.

The active hydrogen atom-containing component constituting the prepolymer (a) may further contain one or more other active hydrogen atom-containing compounds (a3). Examples of (a3) include a monofunctional compound (a31) and a polyfunctional compound (a32).

Examples of (a31) include monools (a311) and primary and secondary monoamines (a31
2).

(A311): monohydric alcohols such as hydrocarbyl alcohol [lower alcohols mentioned in (B11) and (B211)]; (poly) ether monool [cellosolves (cellosolve and methyl, butyl, isobutyl) And hexyl cellosolve);
Carbitols (carbitol and methyl and butyl carbitol); diols or monohydrocarbyl ethers of PAGs mentioned in (B312) and (B322); (poly) oxyalkylenediols and monocarboxylic acids of (B323) Monoester and the like.

As (a312), mono- and dihydrocarbylamines (mono- and dialkylamines, etc.) and primary or secondary monoamines containing a tertiary amino group [N, N-di-diamine of the diamine described in (i4)] And N, N, N'-tri-hydrocarbyl substituents].

The polyfunctional compound (a32) has 2 to 8 or more, preferably 2 to 3, F. (A3
As a specific example of 2), polyamine (a321) [(i
42), the aromatic, aliphatic, alicyclic and araliphatic polyamines and polyoxyalkylene polyamines] and the amino alcohol (a322) [(C22
The mono- and dialkanols having 2 to 2 carbon atoms described in 1)
4) Amines (mono and diethanolamine, isopropanolamine, etc.)].

Among (a3), preferred are those having a low molecular weight and having an EW of 400 or less (calculated by hydroxyl value, primary amine value, secondary amine value, etc.).

Among the active hydrogen atom-containing components, (a21)
Is usually at least 50%, preferably 80 to
99%, more preferably 90 to 98%, (a2
The content of 2) is usually 0 to 50%, preferably 1 to 20%.
%, More preferably 2 to 10%, and the content of (a31) and / or (a32) is usually 0 to 10%, preferably 1 to 5%, and particularly preferably 2 to 3%.

In the preparation of the prepolymer (a), a stoichiometric excess of (a1) reacts with the active hydrogen atom containing component, for example, NCO / active hydrogen atom containing group (OH + NH
The equivalent ratio of ( ₂ + NH) is usually 1.3 to 2.2 / 1, preferably 1.4 to 2.0 / 1.

The equivalent ratio of (a31) / (a1) is preferably from 0 to 0.1, more preferably from 0 to 0.05.
The equivalent ratio of [(a22) + (a32)] / (a1) is preferably 0 to 0.1, and more preferably 0 to 0.05.

The production method of the prepolymer (a) may be an ordinary method. The reaction between (a1) and the active hydrogen atom-containing component is as follows:
The temperature is usually 20C to 150C, preferably 60C to 110C. The reaction is performed in the absence or presence of an inert solvent. As the solvent, an organic solvent containing no active hydrogen atom in the molecule (ketones such as acetone and methyl ethyl ketone, ethers such as THF and dioxane) can be used.

(A21) and if necessary (a22),
The active hydrogen atom-containing component comprising (a31) and / or (a32) may be mixed in advance or added sequentially to react with (a1) in one step, or a multi-step reaction [for example, (a21) And (a1) are reacted,
(A22), (a31) and / or a method of reacting with (a32)].

The isocyanate group content (hereinafter abbreviated as NCO content) of the prepolymer (a) is usually 0.5 to 10%, preferably 1.5 to 6%. The prepolymer (a) is
Usually 1,000 to 20,000, preferably 1,300
-10,000, particularly preferably 1,500-6,000
It has a Mn of 0.

The HLB of (a) is preferably 2 to 6.
5, more preferably 4 to 5.8. When the HLB is 2 or more, the dispersion stability of the aqueous dispersion (A) tends to be good, and when the HLB is 6.5 or less, the stability at a low temperature as a fiber treatment agent is further improved. There is a tendency.

In the present invention, HLB is defined by the Oda method, and is based on the conceptual diagram of organic compounds by Dr. Ryohei Oda described in “Synthesis of Surfactant Activity and Its Application” (Maki Shoten, 1957). It has been determined based on this.

In the present invention, examples of the bisulfite (b) for blocking the terminal isocyanate group of the prepolymer (a) include alkali metal bisulfites such as sodium bisulfite and potassium bisulfite, ammonium bisulfite, A mixture of two or more of these is mentioned. Of these, sodium bisulfite is preferred because it is easy to react with (a). (B) is preferably charged beforehand as an aqueous solution, and its concentration is preferably 10
４０40%.

The method for producing the blocked polyurethane (A) in the present invention is not particularly limited. The synthesis of (A) can be achieved by performing a block reaction of (a) with (b) in an aqueous medium (c) in the presence of an emulsifying dispersant (d). The equivalent ratio of (b) to (a) is preferably 0 from the viewpoint that an increase in water dispersibility can be sufficiently exhibited without causing a decrease in water resistance due to the remaining (b) after the treatment of the textile product. 0.9 to 1.3, and more preferably 0.95 to 1.25.

Aqueous medium (c) usable for the block reaction
Is water and a mixture of water and a hydrophilic solvent. As a hydrophilic solvent, the solubility in water at 25 ° C. is 2 (g / 100).
g water), for example, a hydrophilic alcohol [lower alcohol described in (B211)]; an ester having 2 to 5 carbon atoms [methyl acetate, ethyl acetate, propyl acetate, etc.]; Ketone [acetone, methyl ethyl ketone, diethyl ketone, etc.];
[(Poly) ether monool (eg, cellosolve) represented by (a311)]. By using a hydrophilic solvent, the viscosity of the reaction system decreases, and side reactions are easily suppressed. The weight ratio of water / hydrophilic solvent in the mixture of water and hydrophilic solvent is preferably from 1/9 to 99/1.

The amount of the aqueous medium (c) to be used is preferably 20 to 120% [including water used for dissolving (b)], more preferably 30 to 1%, based on the weight of (a).
00%. If it is 20 to 120%, the emulsification and dispersion of (a) and (b) become easy without the viscosity being too high.

Examples of the emulsifying dispersant (d) to be used include nonionic, anionic, cationic and amphoteric low molecular surfactants (d1), high molecular emulsifying dispersants (d2),
And combinations thereof. Specific examples of (d1) include nonionic, anionic, cationic and amphoteric low molecular surfactants described in US Pat. No. 4,331,447 and US Pat. No. 3,929,678. Agents.

The Mn of the polymer type emulsifying dispersant (d2) is usually 3,000 to 1,000,000, preferably 5,000.
0 to 100,000. Examples of (d2) include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives (eg, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose), carboxyl group-containing (co) polymers (eg, sodium polyacrylate), and No. 133423 and JP-A-08-120041, polymer type emulsifying dispersants having a urethane bond or an ester bond [for example, polyester diol (polycaprolactone polyol etc.) and polyether diol (polyethylene glycol etc.) Isocyanate (IPD
I and HDI).

The HLB of the emulsifying dispersant (d) is preferably 1
It is 1-16, more preferably 12-15, and a nonionic low molecular surfactant having high stability even when coexisting with bisulfite during emulsification and dispersion is particularly preferable.

Among the low molecular weight nonionic surfactants,
Preferred are aliphatic alcohols (with 6 to 2 carbon atoms).
0) AO (2-4 carbon atoms) adduct (degree of polymerization = 2-5)
0), polyalkylene glycol esters of fatty acids (10-20 carbon atoms) or AO (2-4 carbon atoms) adducts of similar fatty acids (polymerization degree 2-50), poly (polymerization degree 2-50) oxyalkylene ( C2-4 carbonized styrene (1-20 mol) aryl ether, polyoxyethylene polyoxypropylene polyol (pluronic nonionic surfactant) and combinations thereof,
Further preferred and especially are.

The amount of the emulsifying dispersant is preferably 1 to 10%, more preferably 3 to 8% based on (a). 1
% Or more, the emulsification and dispersion of (a) and (b) become easy, and if it is 10% or less, the shrink resistance of the fiber product is hardly reduced.

The order of addition of (a) and (b) in the blocking reaction is not particularly limited as long as (a) reacts with (b), but adding (b) to (a) is more preferable. It is more preferable than adding (a) in (b). For example, the preferred order of addition of each component is 1) (a), (d), (b) followed by (c); 2) (a), (b), (d) followed by (c);
3) It is (b) after (c), (d) and (a), and more preferably the order of 1). Further, when the emulsifying dispersant is added before (b), when the emulsifying dispersant contains a hydroxyl group, it is preferable to add (b) immediately after adding the emulsifying dispersant. The reaction can be suppressed.

The temperature of the block reaction is preferably from 10 to
The temperature is 60 ° C, more preferably 20 to 40 ° C. The end point of the blocking reaction is when unreacted bisulfite (b) in the blocked reaction product is titrated with an aqueous potassium hydroxide solution, and the bisulfite content becomes equilibrium.

The content of the blocked isocyanate group (—NHCO—SO ₃ M; M is an alkali metal or ammonium cation) in (A) is preferably 1 to 25%, more preferably 3 to 5%, based on (A). 15%
It is.

The aqueous dispersion of the present invention may further contain an electrolyte (C) if necessary. As the electrolyte (C), a salt of a strong acid having a pKa of 2 or less is preferable from the viewpoint of imparting a sufficient polyurethane resin migration preventing effect. Here, pKa is a logarithmic value of the reciprocal of the dissociation constant (Ka) of the acid. Here, it refers to a value at 25 ° C. in an infinitely diluted aqueous solution, and is equal to −logKa.

As (C), 0.01 at 25 ° C.
Molar conductivity of aqueous solution of mol% (Λ) is 110 to 130,
Particularly, those having 110 to 120 S · cm ² · mol ⁻¹ are preferable. Within this range, a sufficient effect of preventing migration of the polyurethane resin during the processing of the fiber product can be exhibited, and the polyurethane hardly precipitates in the aqueous solution of the treating agent or on the squeezing roll such as a mangle.

The symbol S in the unit of Λ represents Siemens, which is a unit of conductance.

The values of the strong acids and their pKa and the values of the molar conductivity (Λ) of the salts are respectively described in II-4 of Revised 4th Edition, “Chemical Handbook”, Basic Edition II (edited by The Chemical Society of Japan: published in 1993).
Pages 17 and II-322, and II-446 to 45
It is described on page 1.

The measurement of Λ was conducted using a conductivity meter “DS-15”.
(Manufactured by Horiba, Ltd.) and using a platinum black plated conductivity electrode at 25 ± 0.2 ° C.

The strong acid includes, for example, HCl (pKa = −
8), HBr (pKa = -9), HI (pKa = -1)
0), HNO ₃ (pKa = −1.8), H ₂ SO ₄ (pK
a ₂ = 1.99), H ₂ S ₂ O ₃ (pKa ₂ = 1.6), H
IO ₃ (pKa = 0.77), phosphinic acid HPH ₂ O
₂ (pKa = 1.23) and H ₂ SeO ₄ (pKa ₂ =
1.70).

Preferred salts are metal salts (C1), for example, salts (C11) of alkali metals (genus IA; Li, Na and K) and other metals [IB metals (Cu and Ag), alkaline earth (II) Metal) (Mg, Ca, Sr)
And Ba) and IIB metals (such as Zn)] (C1
2), and non-metallic salts (C2), such as ammonium salts (C21) and salts of organic bases (C22) [eg, 1
Salts of primary, secondary and tertiary amines (C221), and 4
Quaternary ammonium salt (C222) and the like].

As a specific example of (C1), (C11)
[Na ₂ SO ₄ , K ₂ SO ₄ , NaNO ₃ , NaCl, Na
Br, NaI and Na ₂ S ₂ O ₃ etc.] and (C1
2) [Sr (NO ₃ ) ₂ , Ba (NO ₃ ) ₂ , Ca (N
O ₃ ) ₂ , CaCl ₂ , BaCl ₂ , AgNO ₃ , SrC
l ₂ , CuCl ₂ , Cu (NO ₃ ) ₂ , MgCl ₂ , Mg
(NO ₃ ) ₂ and Zn (NO ₃ ) ₂ .

Preferred amines constituting (C221) include, for example, mono-, di- and trihydrocarbyl (C1-18) and / or hydroxyalkyl (C2-4) amines. Monoalkyl (C2-18) amines include, for example, ethylamine, n-propylamine, n- and isobutylamine, n-hexylamine and n-octylamine.
The dialkyl (C2-C18 alkylamine) amine includes dimethylamine, diethylamine, dibutylamine, dioctylamine, methylbutylamine, ethylbutylamine, methylpentylamine, and the like. Trihydrocarbylamines include trialkyl (2 to 18 carbon atoms) amines and dialkyl (2 carbon atoms).
-18) benzylamine and the like, for example, trimethylamine, triethylamine, tributylamine, dimethylbenzylamine, diethylbenzylamine and the like. Hydroxyalkylamines include alkanolamines such as mono, di and triethanolamine, ethylethanolamine and diethylethanolamine. Amidine compounds include N, N, N'-
Hydrocarbyl-substituted amidines (eg, N, N-dimethyl-N′-benzylformamidine) and cyclic amidines (eg, imidazole (eg, 1-methylimidazole and 1-methylbenzimidazole), imidazoline (1,2-dimethyl) Imidazoline, etc.), tetrahydropyrimidine (1,2-dimethyl-1,4,5,
6-tetrahydropyrimidine, etc.) and diazabicycloalkenes (such as 1,8-diazabicyclo [5,4,0] undecene-7 and 1,5-diazabicyclo [4,3,0] nonene-5), and international patents Application WO95 / 155
72 publication.

As a specific example of (C2), (C21)
[NH4Cl, NH4NO3 and NH4SO4 etc.],
(C221) [2-hydroxyethylammonium chloride, dimethylammonium chloride, trimethylammonium chloride, etc.] and (C222)
[Methyltriethylammonium chloride, tetraethylammonium chloride, methyl quaternized 1-methylimidazole chloride, methyl quaternized 1,2-dimethyl 1,4,5,6-tetrahydropyrimidine chloride, methyl quaternized 1,8-diazabicyclo [5,4,0] undecene-7 chloride and methyl quaternized 1,5-diazabicyclo [4,3,0] nonene-5 and the like, as well as the corresponding nitrates, sulfates and methosulfates.

Among these salts, preferred are metal salts (C1). More preferred are (C11)
(Especially Na ₂ SO ₄ and K ₂ SO ₄ ) and these (C
Twelve combinations. The preferred content of (C11) in (C1) is at least 50%, more preferably at least 80%, from the viewpoint of the effect of preventing migration of the polyurethane resin. Above and below,%
And parts represent weight% and parts by weight, respectively.

The fiber treating agent in the present invention comprises an aqueous dispersion in which a blocked polyurethane (A), a hydrophobic solvent (B) and, if necessary, an electrolyte (C) are dispersed in an aqueous dispersion medium. Water and a mixture of water and a hydrophilic solvent can be used as the aqueous dispersion medium. Preferred hydrophilic solvents include the same ones as in (c) above. The weight ratio of water / hydrophilic solvent in the aqueous dispersion medium is preferably 100/0 to 80/20, and more preferably 100/0 to 90/10.

In the present invention, the amount of the hydrophobic solvent (B) is preferably 2 to 30%, more preferably 3 to 25%, particularly preferably 5 to 20%, based on the weight of (A). When (B) is 2% or more with respect to (A), a dissolved component tends not to remain and stability at low temperatures tends to be improved,
In addition, the effect of preventing migration of the polyurethane during the fiber processing is easily exhibited. On the other hand, when the content is 30% or less, the emulsifying dispersibility of the aqueous dispersion is hardly reduced.

In the present invention, the amount of the electrolyte (C) is
It is preferably 0 to 5%, more preferably 0.5 to 3% based on (A). When the content of (C) is 5% or less, precipitation and aggregation of polyurethane in a fiber treatment agent or on a squeezing roll such as a mangle decreases.

The fiber treating agent of the present invention comprises (A), (B)
It can be produced by a method in which (C) is added as required, and an aqueous medium (D) is further added as needed, followed by emulsification, dispersion and dilution. The aqueous medium (D) to be added is preferably water, but a mixture of the hydrophilic solvent and water mentioned in (c) above may be used. The preferred water / hydrophilic solvent ratio in (D) is 100/0 to 90/10. (B)
The order of addition of (D) and (C), if necessary, is not particularly limited, and (D) is replaced by (B) and (C).
May be added before or between (B) and (C). (B) may be added before the blocking reaction. Among these, a preferred method is to complete the block reaction of (a) and (b), then further add (B) and (D) to emulsify and disperse, and if necessary, add (C) and mix. How to

The fiber treating agent of the present invention may contain a dibasic acid dihydrazide (E) if necessary. Examples of the dibasic acid constituting (E) include carbonic acid and the aforementioned (i3)
And dicarboxylic acids. Specific examples of (E) include carbodihydrazide, hydrazide from aliphatic dibasic acid having 2 to 8 carbon atoms and hydrazine [glutaric hydrazide (hereinafter abbreviated as GD), succinic hydrazide,
Adipic acid hydrazide (hereinafter abbreviated as AD)],
Hydrazides derived from aromatic dibasic acids and hydrazine (such as isophthalic hydrazide and terephthalic hydrazide). Of these, hydrazide from aliphatic dibasic acid is preferred in terms of the texture of the treated fiber product. In the present invention, the equivalent ratio of the hydrazide group of (E) to the blocked isocyanate group of (A) is usually 0.1.
It is 1-0.7, preferably 0.2-0.5. When the equivalent ratio is 0.1 or more, the water resistance of the fiber product is further improved, and when the equivalent ratio is 0.7 or less, the texture of the treated cloth becomes more flexible. The order of addition of (E) is preferably (A),
After (B), (C) and (D).

The fiber treating agent of the present invention may further comprise, if necessary, a known antifoaming agent and / or wetting agent (HLB 12 to 18).
May be added.
The proportion of these additives is preferably 1% or less, especially 0.1 to 0.5% based on (A).

Examples of the composition of the fiber treating agent in the present invention are as follows. Blocked polyurethane (A): usually 10 to 50%, preferably 15 to 45%, hydrophobic solvent (B): usually 0.2 to 15%, preferably 0.3 to 13%, electrolyte (C): usually 0-2.5%, preferably 0.1-
1.5%, [(B) + (C)]: usually 0.2 to 17.5%, preferably 0.4 to 14.5%, dibasic dihydrazide (E): usually 0 to 8%, Preferably 0.1 to 5%, total of (A) to (D): usually 11 to 65%, preferably 16 to 55%, emulsifying dispersant (d): usually 0 to 5%, preferably 0.3. ~
4%, solid content concentration: usually 10 to 70%, preferably 15 to 60
%, Aqueous medium [(c) + (D)]: usually 30 to 90%, preferably 40 to 85%. Above and below, the solids content is 45% at 130 ° C.
This is the evaporation residue after minute drying. The viscosity (25 ° C.) of the fiber treating agent of the present invention is usually 10 to 1000 mPa · s.

A pH adjuster may be added to adjust the pH of the fiber treating agent to 6 to 9. As a pH adjuster,
Alkaline substances [such as strong base salts (such as alkali metal salts) of weak acids (such as carbonic acid and phosphoric acid) with a pKa of more than 2 such as sodium bicarbonate] and acidic substances such as carbonic acid.

The fiber treating agent of the present invention may be used in combination with other fiber treating agents, for example, various resin emulsions and / or softeners. As a resin emulsion,
Polyurethane emulsions other than (A), acrylic emulsions, SBR latex, and two or more of these. Examples of the softener include a silicone softener (such as an amino group-containing silicone emulsion). These combined ratios in the combined use are preferably 100% based on the weight of the fiber treating agent (solid content) of the present invention.
Or less, more preferably 70% or less.

The fiber treating agent of the present invention can be applied to natural fibers, regenerated fibers, synthetic fibers and the like. Examples of the natural fiber include wool, cotton, silk, and the like.
Regenerated fibers include rayon and acetate. Examples of the synthetic fibers include polyester, polyamide, and polyacrylonitrile. The form of the textile product to be treated includes knitted fabric, woven fabric and non-woven fabric. Among them, it is particularly preferably used as a treatment agent for imparting a soft texture and shrink resistance to a woven fabric of natural fibers (particularly wool).

Examples of the method for applying the fiber treating agent of the present invention to a fiber product include the following methods. (1) The fiber treating agent is diluted with water to prepare a treating agent diluent. (2) The treatment agent diluent is attached to the textile. (3) Squeeze with a mangle until the required amount of adhesion is reached. (4) Heat treatment after pre-drying. The solid concentration of the diluent is usually 1 to 5%. Examples of the method for attaching the diluent include roll coating, dipping, dipping and spraying. The amount of diluent attached is usually 2 to 100
g / 100 g fiber. Predrying is, for example, 80 to 13
0 ° C. for 2 to 5 minutes, heat treatment at 130 to 170 ° C. for 1 minute
３3 minutes. The total amount (solid content after heat treatment) of the total of (A) + (C) + (E) among the treatment agents for textile products is usually 0.5 to 5%, preferably 0.5 to 5%, based on the textile products before treatment. Is 0.8 to 4.5%.

When other fiber treating agents are mixed in advance or used separately with the fiber treating agent of the present invention, the total amount of these fiber treating agents attached to the fiber product (solid content after heat treatment) is And usually 0.5 to 10%, preferably 0.8 to 9 based on the fiber product before treatment.

[0126]

EXAMPLES The present invention will be further described below with reference to Production Examples and Examples, but the present invention is not limited thereto. All parts represent parts by weight.

Production Example 1 PBD was placed in a closed reaction vessel equipped with a thermometer and a stirrer.
(Hydroxyl equivalent EW = 1,000, average number of functional groups F = 2)
147.5 parts of HDI and 24.8 parts of HDI (NC
O / active hydrogen = 2.0). After replacing the reaction system with nitrogen gas, the mixture was reacted under stirring at 105 ° C. for 6 hours to obtain an NCO-terminated urethane prepolymer having an NCO content of 3.8% and an HLB of 2.2. The obtained urethane prepolymer was cooled to 30 ° C., and polyoxyalkylene (EO)
19 mol and PO 1.5 mol block adduct) styrenated (styrene 2.75 mol) phenyl ether (HL
B = 13.8) 13 parts, aqueous sodium bisulfite solution (Na ₂
13.9 parts as S ₂ O ₅ /32.4 parts of water) and 74.7 parts of ethyl alcohol were added. Thereafter, the mixture was stirred at 30 ° C. for 90 minutes to obtain a blocked polyurethane resin (A1). Production Example 2 PBD59 instead of PBD147.5 similar to Production Example 1
Part and glycerin PO adduct (EW = 1,000, F
= 3) A blocked polyurethane (A2) was obtained in the same manner as in Production Example 1 except that 88.5 parts were used. The urethane prepolymer has an NCO content of 3.7% and an HLB of 3.
It was 8. Production Example 3 In place of 59 parts of PBD, PTMG (EW = 1,000, F
= 2) A blocked polyurethane (A3) was obtained in the same manner as in Production Example 2 except that 59 parts were used. The urethane prepolymer has an NCO content of 3.8% and an HLB of 5.7.
Met.

Examples 1 to 11 306.3 parts of (A) described in Table 1 were added to the solvent 2 described in Table 1.
3.4 parts were mixed. Further, 776.3 parts of water and, if necessary, a salt shown in Table 1 were added and mixed for 30 minutes. If necessary, (E) shown in Table 1 was further added and further mixed to obtain an aqueous dispersion. These were used as the fiber treatment agents of Examples 1 to 11. Table 1 shows the analysis values of the solid content and the viscosity (at 25 ° C.).

Comparative Example 1 To 306.3 parts of (A) shown in Table 1, 776.3 parts of water was added and mixed for 30 minutes to obtain an aqueous dispersion. This was used as the fiber treating agent of Comparative Example 1. Table 1 shows the analysis values of the solid content and the viscosity (at 25 ° C.). Comparative Example 2 306.3 parts of (A) shown in Table 1 was added to solvent 2 shown in Table 1.
3.4 parts were mixed. Add 776.3 parts of water and add 3
The mixture was mixed for 0 minutes to obtain an aqueous dispersion. This was used as the fiber treating agent of Comparative Example 2. Table 1 shows the solid content and viscosity (2
5 ° C.). DEK in Table 1 is an abbreviation for diethyl ketone (solubility: 3.4). Comparative Examples 3 and 4 776.3 parts of water and the salt shown in Table 1 were added to 306.3 parts of (A) shown in Table 1 and mixed for 30 minutes, and if necessary, (E) shown in Table 1 was added. And further mixed to obtain an aqueous dispersion. These were used as fiber treatment agents of Comparative Examples 3 and 4. Table 1 shows the analysis values of the solid content and the viscosity (at 25 ° C.). In addition, NaAc is sodium acetate (p of acetic acid).
Ka = 4.56).

[0130]

[Table 1]

Performance test example: A performance test was performed using the fiber treating agents according to the following test methods. Table 2 shows the test results.

Performance Test Example 1 (Test for Sedimentation Stability of Fiber Treatment Agent) The fiber treatment agent was allowed to stand at 10 ° C., and the number of days until sediment was generated was measured visually.

Performance Test Example 2 (Bending Rigidity Test of Treated Fabric) (1) Preparation of Fiber Treatment Agent Diluent 150 parts of fiber treatment agent, penetrant (separate having 12 to 14 carbon atoms)
2 parts of c-alcohol EO (9 mol), 1 part of sodium hydrogen carbonate and 847 parts of water were mixed to prepare a fiber treatment agent diluent (diluent-1). 100 parts of a fiber treatment agent, 2 parts of a penetrant (sec-C12-14 sec-alcohol EO 9 mol adduct), 1 part of sodium hydrogen carbonate, and 897 parts of water are mixed, and a fiber treatment agent diluent (diluent-2) It was created. (2) Undyed wool surge (dimensions 25 cm x 25 c)
m) with a fiber treatment agent diluent (diluent-1 or diluent-
It was immersed in 2) and adjusted by a mangle so as to have a drawing ratio of 60%. This dipped cloth was dried and heat-treated at 130 ° C. for 5 minutes to prepare a treated cloth. Each treatment cloth is 20cm x 20c
m and left for 3 hours under the conditions of 25 ° C. and 50% humidity, and the flexural rigidity of the treated cloth was measured with a KES pure bending tester. A smaller value indicates a softer texture.

Performance Test Example 3 (Area shrinkage rate of treated cloth after washing with detergent) A treated cloth obtained in the same manner as in Performance Test Example 2 was 20 cm ×
It was cut to 20 cm, washed under the following conditions, and the area shrinkage was measured. Washing conditions are JISL-1027, 103
Household detergent 2g / L, bath ratio 1 according to the law
/ 60, wash with warm water of 40 ° C for 5 minutes, rinse for 2 minutes,
After dehydration, repeat washing with horizontal drying at 60 ° C once 2
This was performed 0 times, 40 times, and 60 times, and the area shrinkage after washing was measured. The area shrinkage rate (%) is defined as the area shrinkage rate, where L1 is the distance between markers in the vertical direction, L2 is the distance between markers in the horizontal direction, and L1 ′ and L2 ′ are the distances between markers after a predetermined number of washings of the pre-washed cloth. L1 × L2-L1 ′ × L2 ′) × 100 / (L
1 × L2).

[0135]

[Table 2]

[0136]

The fiber treating agent containing the hydrophobic solvent (B) of the present invention is stable even at low temperatures and has no precipitate, so that it can be treated uniformly at the time of finishing the fiber product. Therefore, the obtained fiber product can exhibit a soft texture and an excellent shrink resistance. Further, since the fiber treatment agent to which the electrolyte (C) is added as required has almost no migration of the polyurethane resin, the above-mentioned feeling and the effect of shrinkage can be further improved. Because of these effects, the fiber treating agent of the present invention is useful as a finishing agent for textile products such as knitted fabrics, woven fabrics, and nonwoven fabrics made of natural fibers, regenerated fibers, synthetic fibers, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 13/148 D06M 13/148 13/224 13/224 13/422 13/422 // C08G 18/00 C08G 18/00 C 18/80 18/80 F term (reference) 4J034 AA01 AA06 BA08 CA03 CA04 CA05 CC02 CC03 CC12 CC61 CC67 DA01 DB03 DF02 DF14 DF19 DF20 DG03 DG04 DP18 DP19 HA01 HA07 HA08 HC03 HC12 HC13 HC17 HC22 HC35 HC64 HC65 HC67 HC71 HD13 QC05 RA09 4L033 AA01 AA04 AB04 AC02 BA01 BA05 BA09 BA11 BA12 BA21 CA50 DA02

Claims (13)

[Claims] 1. A blocked polyurethane (A) obtained by blocking an isocyanate-terminated urethane prepolymer (a) with a bisulfite (b) and a solubility (g) of not more than 2 at 25 ° C.
/ 100 g water), comprising a water-based dispersion containing a hydrophobic solvent (B) having the following properties. 2. The fiber treating agent according to claim 1, wherein (a) has an HLB of 2 to 6.5. 3. The method according to claim 1, wherein (B) is 2 to 3 based on the weight of (A).
3. The fiber treating agent according to claim 1, which contains 0%. 4. (B) is a hydrophobic alcohol (B1),
Claims: It is at least one hydrophobic solvent selected from the group consisting of esters (B2), ethers (B3), ketones (B4), hydrocarbons (B5) and halogenated hydrocarbons (B6). The fiber treatment agent according to any one of claims 1 to 3. 5. (B) is (B1), (B2), (B3)
The fiber treating agent according to claim 4, which is at least one or more hydrophobic solvents selected from the group consisting of (B4) and (B4). 6. (B1) is an aliphatic monohydric alcohol, (B1)
The fiber treating agent according to claim 5, wherein 2) is an aliphatic carboxylic acid alkyl ester, (B3) is a glycol monoalkyl ether, and (B4) is a dialkyl ketone. 7. The aqueous dispersion further contains an electrolyte (C), wherein (C) is a salt of an acid having an acid dissociation constant pKa of 2.0 or less, wherein the salt is a 0.01 mol% aqueous solution. Molar conductivity of 110-130 S · cm ² · mol ^-1 at 25 ° C.
The fiber treatment agent according to any one of claims 1 to 6, further comprising: 8. The fiber treating agent according to claim 7, wherein (C) is an inorganic salt of a strong acid and a base. 9. The method according to claim 1, wherein (C) is 0.5% based on the weight of (A).
The fiber treating agent according to claim 7, which contains about 5% to about 5%. 10. The dibasic dihydrazide (E)
The fiber treating agent according to any one of claims 1 to 9, further comprising: 11. A method for treating or processing a fiber product, comprising treating the fiber product with the fiber treatment agent according to any one of claims 1 to 10. 12. A method for treating or processing a fiber product, comprising subjecting a fiber product immersed and treated with the fiber treatment agent according to claim 1 to a heat treatment. 13. A fiber product processed with the fiber treatment agent according to claim 1.