JP2000265374A - Textile treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject agent capable of imparting textile products with soft touch and shrinkproofness after laundered with detergent. SOLUTION: This textile treatment agent consists of an aqueous dispersion containing, as the essential components, (A) a block form, using (b) a bisulfite, of (a) an isocyanate-terminated urethane prepolymer derived from (a1) an organic polyisocyanate, (a2) a polymeric polyol 400-2,000 in hydroxyl equivalent, and, as necessary, (a3) an active hydrogen group-contg. low-molecular polyfunctional compound, and (B) an emulsifier, and is characterized by being 2-6.5 in the HLB number of the urethane prepolymer (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fiber treatment agent. More specifically, the present invention relates to a fiber treatment agent used for processing a textile product such as a woven fabric.

[0002]

2. Description of the Related Art A water-soluble polyurethane in which isocyanate groups of a urethane prepolymer are blocked with bisulfite has been known as a fiber treatment agent for preventing shrinkage of a woven fabric after washing with a detergent. For example, Shoko 5
No. 0-155794).

[0003]

However, the fabric treated with such a water-soluble polyurethane has a problem that the texture becomes hard. SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber treatment agent capable of achieving both a soft feeling and prevention of shrinkage after washing with a detergent.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to obtain a fiber treatment agent which solves the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to an isocyanate group-terminated urethane derived from an organic polyisocyanate (a1), a high molecular weight polyol having a hydroxyl equivalent of 400 to 2,000 (a2) and, if necessary, an active hydrogen group-containing low molecular weight polyfunctional compound (a3). The urethane prepolymer (a) has an HLB of 2 to 6.5 and comprises an aqueous dispersion containing a block (A) of the prepolymer (a) formed by bisulfite (b) and an emulsifier (B) as essential components. It is a fiber treatment agent characterized in that there is.

In the present invention, the organic polyisocyanate (a1) constituting the urethane prepolymer (a) has 2 carbon atoms (excluding carbon in the NCO group, hereinafter the same).
To 12 aliphatic diisocyanates [eg, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, etc.]; alicyclic diisocyanates having 4 to 18 carbon atoms [eg, 1,4-cyclohexane diisocyanate (CD
I), isophorone diisocyanate (IPDI), 4,
4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), adamantane disocyanate, etc.]; 8 to 15 araliphatic diisocyanates [for example, xylylene diisocyanate (XDI), α,
α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like]; an aromatic polyisocyanate having 6 to 20 carbon atoms [eg, 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate] (TDI), diphenylmethane-2,4′- or 4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, o-tolidine diisocyanate, Crude TDI, polyphenylmethane polyisocyanate (crude MDI), etc.]; and mixtures of two or more of these. Preferred among these are aliphatic diisocyanates, alicyclic diisocyanates and araliphatic diisocyanates in that the treated fibers do not discolor, and more preferred are aliphatic diisocyanates in terms of the texture of the treated fabric.

The polymer polyol (a) constituting (a)
Examples of 2) include polyoxypropylene and / or oxybutylene polyol (a), polyester polyol (b), polyolefin polyol (c), polymer polyol (d), and a mixture of two or more of these. The hydroxyl equivalent of (a2) is usually from 400 to 200.
0, preferably 500-1700. If the hydroxyl group equivalent is less than 400, the texture of the treated fabric may be too hard, and if it exceeds 2,000, the fabric may have reduced shrink resistance. The average number of functional groups of (a2) is preferably 2.3 to 3, particularly preferably 2.4 to 2.9, from the viewpoint of the texture and shrinkage resistance of the treated fabric.

The polyoxypropylene and / or oxybutylene polyol (a) includes polyhydric alcohols [ethylene glycol, propylene glycol, 1,3
-Butylene glycol, 1,4-butanediol, 1,
Dihydric alcohols such as 6-hexanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, xylylene glycol; glycerin, trimethylolpropane Trihydric alcohols such as pentaerythritol,
Diglycerin, pentaerythritol, diglycerin,
α-methylglucoside, sorbitol, xylit, mannitol, tetrahydric or higher polyhydric alcohol such as dipentaerythritol, etc.), polyhydric phenol [pyrogallol,
Monocyclic dihydric phenols such as catechol and hydroquinone;
Bisphenols such as bisphenol A, bisphenol F and bisphenol S], amines [ammonia; alkylamine having 1 to 20 carbon atoms (butylamine,
Monoamines such as octylamine) and aniline;
Aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine and diethylenetriamine; piperazine, N-aminoethylpiperazine and other heterocyclic polyamines described in JP-B-55-21044; oils such as dicyclohexylmethanediamine and isophoronediamine Cyclic polyamines; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine,
Aromatic polyamines such as diphenyl ether diamine;
Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine]] and a compound having a structure in which an alkylene oxide having 3 to 4 carbon atoms is added to a polyfunctional compound having an active hydrogen atom. A mixture of the above is mentioned. Of these, preferred are alkylene oxide adducts of dihydric trihydric alcohols and / or polyhydric phenols.

The alkylene oxides include propylene oxide (hereinafter abbreviated as PO), 1,2-,
2,3-, 1,3- or 1,4-butylene oxide, and a combination system (random and / or block) of two or more thereof. In addition to these, ethylene oxide (hereinafter abbreviated as EO) may be used in a small amount (for example, 10% by weight or less, preferably 5% by weight or less in all alkylene oxides) as long as the object of the present invention is not impaired.

As the polyester polyol (b),
For example, one or more of the above-mentioned dihydric alcohols and a dicarboxylic acid [aliphatic dicarboxylic acids having 4 to 12 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.), aromatics having 8 to 16 carbon atoms] Condensed polyester polyols derived from dicarboxylic acids (such as isophthalic acid and terephthalic acid) and their ester-forming derivatives [anhydrides, lower alkyl (C1-4) esters and the like] [eg, poly (ethylene adipate) ) Diol, poly (butylene adipate) diol, poly (hexamethylene adipate) diol, poly (neopentyl adipate) diol, poly (ethylene / butylene adipate) diol, poly (neopentyl / hexyl adipate) diol, poly (3-methylpentyl) Adipate)
Diols, poly (butylene isophthalate) diols, etc.];
Polylactone polyols obtained by polyaddition of lactones (γ-butyrolactone, ε-caprolactone, γ-valerolactone, etc.) (for example, polycaprolactonediol or triol, polyvalerolactonediol or triol, poly-3-methylvalero) Lactone diol or triol, etc.); polycarbonate polyols (for example, polyhexamethylene carbonate diol, etc.) derived from one or more of the above-mentioned dihydric and trihydric alcohols and carbonates (dimethyl carbonate, ethylene carbonate, etc.); A mixture of the above is mentioned.

The polyolefin polyol (c) includes, for example, polybutadiene polyol, polyisoprene polyol and hydrogenated products thereof.

The polymer polyol (d) includes radically polymerizable monomers [for example, styrene, (meth) acrylonitrile, (meth) acrylate, vinyl chloride) in the polyol (the polyether polyol and / or the polyester polyol). , A mixture of two or more of these, etc.] and finely dispersing the polymer (polymer content is usually 5 to 30% by weight).

Preferred examples of the polymer polyol (a2) include (a), (b),
(C) and a combination of two or more of these.

The active hydrogen group-containing low molecular weight polyfunctional compound (a3) optionally used together with (a2) includes:
Polyhydric alcohols having 2 to 15 carbon atoms [dihydric alcohols (eg, ethylene glycol, propylene glycol,
Neopentyl glycol, 1,4-butanediol, diethylene glycol, etc.); trihydric alcohols (eg, glycerin, trimethylolpropane, etc.); low molar addition products of these polyhydric alcohols with alkylene oxides (EO and / or PO) (hydroxyl equivalents) Less than 400)], diamines having 2 to 10 carbon atoms (eg, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, etc.); hydrazine or its derivatives (eg, dibasic dihydrazide, eg, adipic dihydrazide). can give. The amount of (a3) used is usually 20% by weight or less, preferably 15% by weight or less based on the total weight of (a2) and (a3).

As the component (a), a chain terminator can be used, if necessary, in addition to the component (a2) and, if necessary, (a3). Examples of the chain terminator include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, dibutylamine) , Alkylamines such as monooctylamine; alkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

Equivalent ratio of (a1) to (a2) and optionally (a3) constituting isocyanate group-terminated urethane prepolymer (a) (NCO / active hydrogen-containing group ratio)
Is the ease of blocking reaction with the bisulfite (b),
From the viewpoint of the washing resistance and texture of the treated fiber,
3 to 2, particularly preferably 1.4 to 1.9. The isocyanate group content of (a) is usually 1 to 7% by weight,
Preferably it is 2 to 5% by weight.

The HLB of (a) needs to be 2 to 6.5, preferably 3 to 6. HLB
Is less than 2, it is difficult to form the block body (A),
If it exceeds 6.5, the shrink resistance of the treated woven fabric decreases.
The HLB is a value calculated by the method described in, for example, Oda and Yukimura, “Synthesis of Surfactant and Its Application” (Maki Shoten, 1957), page 501.

The production method of (a) is a conventional method and is not particularly limited. For example, organic solvents containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone,
(A1) and the active hydrogen component comprising (a2) and, if necessary, (a3) in the presence or absence of tetrahydrofuran, dioxane, etc., by a one-sit method or a multi-stage method, usually at 20 ° C. to 150 ° C., preferably Is 60
A method in which the reaction is carried out at a temperature of from 110 ° C to 110 ° C.

In the prepolymerization reaction, a catalyst usually used for polyurethane can be used to accelerate the reaction. Examples of such catalysts include metal catalysts such as tin-based catalysts [trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannas octoate, dibutyltin maleate, etc.], and lead-based catalysts. Catalysts [lead oleate, 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.], other metal catalysts [metal naphthenates such as cobalt naphthenate,
Phenylmercury propionate, etc.]; and amine catalysts such as triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,
4,0] undecene-7 [DBU (manufactured by San Apro, registered trademark)] etc .; dialkylaminoalkylamines [dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropyl Carbonates and organic acid salts (such as formate) of aminopropylamines and the like and heterocyclic aminoalkylamines [such as 2- (1-aziridinyl) ethylamine and 4- (1-piperidinyl) -2-hexylamine] ;
N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine and the like; and a combination of two or more of these. The amount of these catalysts used is usually 3% by weight or less, preferably 0.001 to 2%, based on the weight of (a).
% By weight.

In the present invention, the bisulfite (b) used for blocking the isocyanate group in (a) includes:
Examples thereof include sodium bisulfite, ammonium bisulfite, and potassium bisulfite. Of these, sodium bisulfite is particularly preferred because it easily reacts with (a).

The emulsifier (B) used in the present invention has an average HLB of usually 11 to 16, preferably 12 to 1
5, emulsifiers such as anionic emulsifier, nonionic emulsifier, amphoteric emulsifier, and cationic emulsifier,
When emulsifying (a) to form a block (A), a nonionic emulsifier that is stable even when coexisting with bisulfite (b) is preferable. As such a nonionic emulsifier,
C8-C18 aliphatic monoalcohol alkylene oxide (C2-C4) adduct (e.g., lauryl alcohol EO 6-20 mol adduct, etc.);
Alkylene oxides of up to 18 fatty acids (with 2 carbon atoms)
4) adducts (for example, adducts of lauric acid with EO of 6 to 25 mol); styrenated (1.1 to 10 mol) phenol alkylene oxide (2 to 4 carbon atoms) adducts [for example, styrenated (1.5 to 3 mol) EO1 of phenol
0-25 mol adducts, block adducts of 10-25 mol EO of styrenated (1.5-3 mol) phenol and 1-5 mol PO, etc.); alkylene oxides (2 carbon atoms)
And 4) random and / or block copolymers (for example, an adduct of 40 to 150 mol of EO of polypropylene glycol having a degree of polymerization of 25 to 35);
Combinations of more than one species are mentioned. Preferred of these are and, and particularly preferred are and. The amount of (B) used is 1 to 10% by weight, especially 3 to 8% by weight, based on the weight of (A), in view of the ease of forming the block (A) and the shrink resistance of the treated fabric. % By weight is preferred.

The fiber treating agent of the present invention is, for example, (a)
An aqueous solution of (b) (concentration: 20 to 40% by weight) is added to the mixture of (B) and (B), and the mixture is thoroughly mixed and reacted at usually 10 to 60 ° C., preferably 20 to 40 ° C. to form a block (A). Water alone or water and a water-soluble organic solvent [alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (tetrahydrofuran, dioxane, etc.), amides (dimethylformamide, N -Methylpyrrolidone) and a mixture of two or more thereof. The water-soluble organic solvent may be previously mixed in the block (A). (B) for the above blocking reaction
Is usually 9 to the isocyanate group of (a).
It is 0 to 130 equivalent%, preferably 95 to 125 equivalent%. The blocking ratio of the isocyanate group of (a) in the block body (A) by (b) is usually at least 90%, preferably 95 to 100%. If the blocking ratio is less than 90%, the water dispersibility of (A) decreases. If necessary, a trace amount of the remaining isocyanate group may be reacted with the above-mentioned chain terminating agent (for example, monoamine) to be blocked.

The fiber treating agent of the present invention may contain, if necessary, known defoaming agents, wetting agents, various resin emulsions (polyurethane emulsion, acrylic emulsion, SBR latex, etc.), softening agents and the like. In the case of a resin emulsion, the compounding amount thereof is preferably 30% by weight or less, especially 20% by weight or less based on the weight of the block body (A) in terms of solid content, and in the case of other additives (A) Is preferably 1% by weight or less, particularly preferably 0.1 to 0.5% by weight based on the weight of

The solid content concentration of the fiber treating agent of the present invention is not particularly limited, but is usually 10 to 50% by weight, preferably 15% by weight.
~ 45% by weight. The viscosity (25 ° C.) is usually 10
１０００1000 mPa · s.

The fiber treating agent of the present invention includes natural fibers such as wool, cotton and silk; regenerated fibers such as rayon and acetate; fibers such as knitted fabrics, woven fabrics and non-woven fabrics such as synthetic fibers such as polyester, polyamide and polyacrylonitrile. Can be applied to products. Among them, it is particularly suitably used as a treatment agent for imparting a soft texture and shrink-proofing property to natural fiber (especially wool) fabrics.

As a method for applying the fiber treating agent of the present invention to textiles, the treating agent may be used at a required concentration (usually 1 to 5).
% By weight), adhere to the textile by roll coating, dipping, dipping, etc., squeeze to the required amount of adhesion with a mangle or the like, pre-dry at 100-130 ° C. for 3-5 minutes, A method of performing a heat treatment at 130 to 150 ° C. for 1 to 3 minutes is exemplified. The adhesion amount (solid content) of the treating agent to the textile is usually 1 to 5% by weight based on the weight of the textile before the treatment.

[0026]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following, "parts" indicates parts by weight and "%" indicates% by weight.

Example 1 In a closed reaction vessel equipped with a thermometer and a stirrer, polybutadiene having a hydroxyl equivalent of 1660 in which PO was added to glycerin, 131.1 parts of a triol having 3 functional groups, a hydroxyl equivalent of 500, and a functional group of 2 were added. 26.2 parts of glycol (average number of functional groups of the polyol: 2.5) and 20.9 parts of HDI were charged, and the reaction system was replaced with nitrogen gas.
The mixture was reacted at 6 ° C. for 6 hours to obtain an NCO-terminated urethane prepolymer having a free isocyanate group content (hereinafter, referred to as NCO content) of 2.7% and an HLB of 5.1. The obtained urethane prepolymer was cooled to 30 ° C., and an emulsifier (H) obtained by adding 19 mol of EO and 1.5 mol of PO to 1 mol of styrenated (2.75 mol) phenol was added.
(LB = 13.8) 28 parts, an aqueous solution of sodium bisulfite (11.7 parts of sodium bisulfite / 29.3 parts of water) and 133.5 parts of ethanol were added and mixed at 30 ° C. for 30 minutes to complete the reaction. Further, 2000 parts of water was added thereto and mixed for 30 minutes, and the solid content was 20% and the viscosity was 50 mPa · s.
Thus, 1000 parts of an aqueous polyurethane resin dispersion at a temperature of / 25 ° C were obtained. This aqueous urethane resin dispersion was diluted with water so as to have a solid content of 3%, and the pH was adjusted to 7 with sodium bicarbonate to obtain a treating agent liquid (A1).

Example 2 Example 1 was repeated except that the polybutadiene glycol was replaced with the same amount of polytetramethylene ether glycol having a hydroxyl equivalent of 500 and a functional group number of 2 (urethane prepolymer HLB = 5.7). By the same operation as described above, a treating agent liquid (A2) having a solid content of 3% was obtained.

Example 3 A urethane prepolymer having an NCO content of 2.3% and an HLB of 5.6 was prepared from 163.5 parts of a triol having a hydroxyl equivalent of 1660, a functional group having 3 functional groups and 16.5 parts of HDI obtained by adding PO to glycerin. Obtained. A treating agent solution (A3) having a solid content of 3% was obtained in the same manner as in Example 1 except that 32.5 parts of 25% sodium bisulfite was used.

Comparative Example 1 A treating agent solution was obtained by the following method according to the description in Example 1 of JP-A-50-155794. EO was added to polypropylene glycol (average molecular weight: 1200) to give an average molecular weight of 2400, 21 parts of a block copolymerized polyether diol (hydroxyl value: 46.7), adipic acid / 1,6-
Hexanediol / neopentylglycol (molar ratio 10: 7: 4) polyester diol (having a hydroxyl value of 45.
1, acid value 2.4) 56 parts, 1.6-hexanediol 3
Part and HDI 20 parts were reacted at 100 to 105 ° C. for 1 hour to obtain a prepolymer (NCO content 5.1%, H
LB 7.8) was cooled to 40 ° C., and 20 parts of dioxane was added to adjust the viscosity. Then, 65 parts of a 25% aqueous sodium bisulfite solution was added and mixed to complete the blocking reaction, and 220 parts of water was further added to dilute to obtain a 30% solids aqueous urethane resin dispersion. This aqueous dispersion was diluted with water so as to have a solid content of 3% to obtain a treating agent liquid (A4) for comparison.

Test Fabric Preparation Example The treating agent liquid (A) obtained in Examples 1 to 3 and Comparative Example 1
1) to (A4) and using only water as a blank,
A test cloth was prepared by the following method. Undyed wool muslin (dimensions 25 cm × 25 cm) for the test was immersed in the treating solution and adjusted with a mangle so that the drawing ratio was 100%. This dipped cloth is pre-dried at 130 ° C. for 3 minutes, and further dried for 150 minutes.
Heat treatment was performed at 1 ° C. for 1 minute to prepare a treated cloth.

Performance Test Example 1 (Bending Rigidity Test of Treated Cloth) Each treated cloth obtained in the above-mentioned preparation example was cut into a piece of 20 cm × 20 cm, left at a temperature of 25 ° C. and a humidity of 50% for 3 hours. The bending stiffness of the treated cloth was measured with a pure bending tester. The results are shown in Table 1.

[0033]

[Table 1]

Performance Test Example 2 (Example of Measurement of Area Shrinkage Ratio of Treated Cloth after Washing with Detergent) Each of the treated cloths obtained in the above preparation example was cut into 20 cm × 20 cm, washed under the following conditions, and washed 20 times and 40 times. And 60
The area shrinkage after the first washing was measured. The results are shown in Table 2. The washing conditions were JISL-0217-1976.
2g / household detergent in a home washing machine according to the 103 method
L, bath ratio 1/30, washing with warm water at 40 ° C. for 5 minutes, rinsing for 2 minutes, and after dehydration, washing was repeatedly performed with horizontal drying at 60 ° C. once.

[0035]

[Table 2]

From Table 1, it can be seen that the treating agents (A1 to A3) of the present invention of Examples 1 to 3 give a softer texture than the treating agent (A4) of Comparative Example 1. Table 2 also shows that the treating agent of the present invention provides excellent shrink resistance even after washing.

[0037]

Industrial Applicability The fiber treating agent of the present invention can impart a soft texture and excellent shrink resistance to textiles such as textiles. Since the fiber treatment agent of the present invention exhibits the above effects,
It is useful as a finishing agent for textiles such as natural fibers such as wool, cotton and silk, regenerated fibers such as rayon and acetate, synthetic fibers such as polyester, polyamide and polyacrylonitrile, knitted fabrics, woven fabrics and nonwoven fabrics.

Claims (6)

[Claims] 1. An organic polyisocyanate (a1) and a polymer polyol (a) having a hydroxyl equivalent of 400 to 2,000.
2) and, if necessary, an isocyanate group-terminated urethane prepolymer (a) derived from an active hydrogen group-containing low molecular weight polyfunctional compound (a3) and a bisulfite (b) block (A) and an emulsifier (B). The urethane prepolymer (a) comprises an aqueous dispersion as an essential component,
A fiber treating agent, wherein B is 2 to 6.5. 2. The fiber treating agent according to claim 1, wherein (a2) is at least one selected from polypolyoxypropylene and / or polyoxybutylene polyol, polyester polyol and polyolefin polyol. 3. The fiber treating agent according to claim 1, wherein the average number of functional groups in (a2) is 2.3 to 3. 4. (a) Constituting (a) (a1) / [(a2)
+ (A3)] is an equivalent ratio of (1.3 to 2) / 1, the fiber treating agent according to any one of claims 1 to 3. 5. The fiber treating agent according to claim 1, wherein (B) is a nonionic emulsifier having an average HLB of 11 to 16. 6. The amount of (B) is 1 based on the weight of (A).
The fiber treatment agent according to any one of claims 1 to 5, which is 10 to 10% by weight.