JP3626418B2 - Textile treatment agent - Google Patents

Description

【００５０】
【発明の効果】
本発明の繊維処理剤は、一回の処理で織物などの繊維製品に柔軟な風合いと優れた防縮性を与えることができる。
上記効果を奏することから本発明の繊維処理剤は、羊毛、木綿、絹等の天然繊維、レーヨン、アセテート等の再生繊維、ポリエステル、ポリアミド、ポリアクリロニトル等の合成繊維等の織物、編物、不織布などの繊維製品の仕上げ剤として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber treatment agent. More specifically, the present invention relates to a polyurethane resin-based fiber treatment agent used for finishing processing of textile products such as knitted fabrics, woven fabrics and nonwoven fabrics.
[0002]
[Prior art]
In the field of fiber treatment agents using a polyurethane resin, there is a problem that the polyurethane resin undergoes migration during the finishing process, and the texture becomes hard due to this. As a technique for improving this, there has been proposed a method for preventing migration of a polyurethane resin by once treating a fiber product with a polyurethane resin and then immersing it in an electrolyte aqueous solution. For example, JP-A-6-33397.
However, even the method disclosed in the above publication has a problem in that migration of the polyurethane resin occurs not a little and the flexibility of the treated fiber product is insufficient.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyurethane resin-based fiber treatment agent that hardly causes migration of a polyurethane resin during finishing of a fiber product, and can give sufficient flexibility and shrinkage resistance to the treated fiber product. .
[0004]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies on a polyurethane resin-based fiber treatment agent comprising a polyurethane resin and an electrolyte, which can impart sufficient flexibility and shrinkage resistance to a fiber product and can be treated in a single treatment step. The present invention has been reached. That is, the present invention is an aqueous liquid containing a polyurethane resin (A) having an ionic group or / and an ion forming group in the molecule and an electrolyte (B), wherein (A) is blocked with bisulfite. It is a polyurethane resin containing an isocyanate group, and a molar conductivity Λ at 25 ° C. of a 0.01 mol% aqueous solution of (B) is 110 to 130 S · cm.²・ Mole^-1And (B) is a salt of an acid having an acid dissociation index pKa of 2.0 or less.
[0005]
The configuration of the present invention will be described in detail below. The polyurethane resin (A) in the present invention is a polyurethane resin containing an ionic group or / and an ion-forming group in the molecule. Examples of the ionic group include an anionic group, a cationic group, and a zwitterionic group. Examples of the anionic group include -COO.⁻, -SO₃ ⁻, -PO₄ ^3-As the cationic group, for example, -N⁺Examples of zwitterionic groups such as -N⁺-CH₂-COO⁻Etc. An ion-forming group is a group that reacts with another compound to form an ion. For example, —COOH, —SO₃H, -H₂PO₄, -NH₂Etc. In the present invention, (A) is a polyurethane resin (A-1) containing an ionic group or / and an ion-forming group at the molecular end and a polyurethane resin containing a molecular side chain or main chain other than the terminal (A-2). ). Moreover, what has in a terminal and a side chain (A-3), what has a terminal and a main chain (A-4), and what has a terminal, a side chain, and a main chain (A-5) may be sufficient. Of these, (A-1) and (A-2) are preferred, and (A-1) is more preferred.
[0006]
As a method for introducing an ionic group or / and an ion-forming group in the case of (A-1), the terminal produced using the polymer polyol (a) and the organic polyisocyanate (b) as essential constituents is an isocyanate group. There is a method in which a certain prepolymer is reacted with a blocking agent (c-1) having an ionic group or / and an ion forming group. Moreover, it can also introduce | transduce by using a dialkylamino alcohol (dimethylaminoethanol, diethylaminoethanol, etc.), an amino acid (glycine, alanine, etc.) and monoaminosulfonic acid (taurine etc.) as a reaction terminator.
(C-1) is a compound containing a functional group that blocks an isocyanate group and an ionic group or / and an ion-forming group in one molecule, and examples of such a compound include an anionic group Examples of the compound having an anion-forming group include bisulfurous acid (salt) [for example, bisulfurous acid and salts thereof (for example, alkali metal salts such as sodium, potassium, lithium, and ammonium salts)].
[0007]
In addition, in the case of (A-2) to (A-5), as a method for introducing an ionic group or / and an ion forming group, a polymer polyol (a), an organic polyisocyanate (b), and two active hydrogens A prepolymer is produced using the compound (d) having ionic group or / and ion forming group and 3 or more as an essential component, and if necessary, an ionic group or / and ion forming is formed on the terminal isocyanate group. There is a method of reacting a blocking agent (c-1) containing a functional group or / and a blocking agent (c-2) containing neither an ionic group nor an ion-forming group with a terminal isocyanate group.
[0008]
Examples of the compound (d) having 2 to 3 or more active hydrogens and an ionic group or / and an ion-forming group used in the production of (A-2) include the following compounds.
(D-1) Compounds having 2 to 3 or more active hydrogens and an anion group or anion-forming group, such as dihydroxycarboxylic acid [tartaric acid, 4,6-dihydroxyisophthalic acid, α, α-dimethylolpropion Acid, α, α-dimethylolbutyric acid, etc.], dihydroxysulfonic acid [1,7-dihydroxynaphthalenesulfonic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, etc.], diaminosulfonic acid [taurine, 2 , 4-diaminobenzenesulfonic acid and the like], dihydroxyalkylsulfamic acid [N, N-bis (2-hydroxyethyl) sulfamic acid, N, N-bis (2-hydroxypropyl) sulfamic acid and the like] and their alkylene oxide additions Product (alkylene having 2 to 4 carbon atoms, addition mole number 1 to 0), and salts thereof (alkali metal salts, amine salts, ammonium salts);
(D-2) Two or more active hydrogens are three or more and a compound having a cation group or a cation-forming group, such as alkoxyamine (N-methyldiethanolamine, N-3-aminopropyldiethanolamine, bis-3- Aminopropyl-butylamine etc.) and salts thereof (hydrochloric acid, sulfuric acid, nitric acid, salts of inorganic acids such as trifluoroboric acid, acetic acid, propionic acid, butyric acid, maleic acid, fumaric acid, benzoic acid, isophthalic acid, terephthalic acid, etc. Of carboxylic acid, ethanesulfonic acid, isethionic acid, vinylsulfonic acid, allylsulfonic acid, p-toluenesulfonic acid and other organic acid salts, methyl chloride, ethyl chloride, propyl chloride, benzyl chloride, etc. Quaternary formed by 18 alkyl halides or halogenated aralkyls Ammonium salt, etc.);
(D-3) a compound having 2 or more active hydrogens and 3 or more and a zwitterionic group or a zwitterion-forming group (which forms a zwitterionic group by reacting with a base or an acid), for example, dialkanol Amino acids (diethanolglycine, diethanolalanine, etc.);
Of these, the compound (d-1) is preferable, more preferably dihydroxycarboxylic acid, and particularly preferably α, α-dimethylolpropionic acid.
Other than (A-1) and (A-2), ionic groups at the terminal and side chain (A-3), terminal and main chain (A-4), and terminal, side chain and main chain (A-5) Alternatively, the introduction method in the case of containing an ion-forming group can be performed by combining the introduction methods (A-1) and (A-2) described above.
[0009]
The amount of the ionic group and / or ion-forming group in the polyurethane resin (A) of the present invention is usually 0.1 to 20% by mass, preferably 0.5 to 15% by mass, based on the mass of (A). %. When the content of ionic groups or / and ion-forming groups is 0.1% by mass or more, a more stable dispersion is obtained, and when the content is within 20% by mass, water resistance after treatment is improved. Here, the mass of the ionic group and the ion-forming group is -COO.⁻, -SO₃ ⁻, -PO₄ ^3-, -N⁺Are calculated as an ionic group and an ion-forming group. Moreover, the weight average molecular weight (measurement by GPC) of (A) is 2000-200000 normally.
[0010]
As the polymer polyol (a) constituting the polyurethane resin (A) of the present invention, polyether polyol (a-1), polyester polyol (a-2), polydiene polyol (a-3), polymer polyol ( a-4) and a mixture of two or more thereof.
The hydroxyl equivalent of (a) is usually from 400 to 2000, preferably from 500 to 1700. When the hydroxyl equivalent is less than 400, there is a problem that the texture of the treated fabric is too hard, and when it exceeds 2000, the shrinkage resistance of the fabric may be lowered.
The average functional group number of (a) is preferably 2.1 to 3, particularly 2.2 to 2.9 from the viewpoint of the texture and shrinkage resistance of the treated fabric.
[0011]
As the polyether polyol (a-1), a low molecular weight polyol having a molecular weight of 62 to 500 [dihydric alcohol (ethylene glycol, propylene glycol, 1,4-butanediol, etc.), dihydric phenol (bisphenol A, etc.), 3 Starting from polyhydric alcohols (glycerin, trimethylolpropane, etc.) as starting materials, alkylene oxides [alkylene oxides having 2 to 4 carbon atoms; ethylene oxide (EO), propylene oxide (PO), 1,2 butylene oxide, tetrahydrofuran, etc.]] Examples thereof include those obtained by polyaddition polymerization or polyaddition copolymerization (block and / or random).
Specific examples of the polyether polyol include, for example, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene (block or random) diol, polyoxytetramethylene glycol (PTMG), polyoxyethylene polyoxytetramethylene (block or random). And glycols and mixtures of two or more of these.
[0012]
As the polyester polyol (a-2), for example, one or more of low molecular weight polyols exemplified as a starting material of polyether polyol and dicarboxylic acid [aliphatic or aromatic dicarboxylic acid having 4 to 12 carbon atoms [aliphatic dicarboxylic acid ( Succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, etc.)] Butylene adipate polyol, polyethylene butylene adipate polyol, etc.], polylactone polyol (polycaprolactone polyol, polyvalerolactone polyol) obtained by ring-opening polymerization of a lactone having 4 to 8 carbon atoms (ε-caprolactone, valerolactone) Etc.), and mixtures of two or more thereof.
[0013]
Examples of the polydiene polyol (a-3) include polybutadiene polyol, polyisoprene polyol, and hydrogenated products thereof.
[0014]
Examples of the polymer polyol (a-4) include radical polymerizable monomers [for example, styrene, (meth) acrylonitrile, (meth) acrylic acid ester, vinyl chloride in the polyol (polyether polyol and / or polyester polyol)]. , A mixture of two or more of these] and the like, and the radical polymer dispersed therein (polymer content is usually 5 to 30% by mass).
[0015]
Among those exemplified as the polymer polyol (a), preferred are (a-1), (a-2), (a-3) and a combination of two or more of these.
[0016]
The organic polyisocyanate (b) constituting the (A) is an aliphatic isocyanate having 2 to 12 carbon atoms (the same applies hereinafter except for carbon in the NCO group) [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 (CDI), isophorone diisocyanate (IPDI), 1,4-dicyclohexylmethane diisocyanate (hydrogenated MDI) ), Methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), adamantane diisocyanate, etc.]; Aliphatic diisocyanates [for example, xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.]; aromatic polyisocyanates having 6 to 20 carbon atoms [for example, 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-dimethylphenylmethane 4,4-diisocyanate, O-tolidine disocyanate, crude TDI, polyphenylmethane polyisocyanate (crude MDI), etc.]; and mixtures of two or more of these. Of these, preferred are aliphatic isocyanates, alicyclic diisocyanates, and aromatic aliphatic diisocyanates in that the treated fibers do not change color, and more preferred are aliphatic diisocyanates in terms of the texture of the treated fabric. is there.
[0017]
The blocking agent used in (A-2) is bisulfite in that hydrophilicity can be imparted to the polyurethane resin.
[0018]
The amount of the blocking agent used is usually 0.05 to 1.1 equivalents as the blocking agent with respect to the equivalent number of isocyanate groups present in the polyurethane prepolymer.
[0019]
In the production of (A) of the present invention, an active hydrogen-containing low molecular nonionic compound (e) may be used together with (a) to (d) if necessary.
As a specific example of (e),
(1) Polyhydric alcohols having 2 to 15 carbon atoms [divalent alcohols (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, diethylene glycol, etc.); trivalent alcohols (for example, glycerin, trimethylol) Propane, etc.); alkylene oxide (EO and / or PO) low molar adducts of these polyhydric alcohols (hydroxyl equivalent 400 or more), etc.],
(2) C2-C10 diamines (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, etc.); hydrazine or its derivatives (dibasic acid dihydrazide, such as adipic acid dihydrazide).
The amount of (e) used is usually 20% by mass or less, preferably 15% by mass or less, based on the total mass of (a) and (e).
[0020]
As a constituent of (A), a chain terminator (f) can be used as necessary. Examples of the chain terminator include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, dioxygen) Mono- or dialkylamines such as butylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).
The amount of (f) used is usually 0.2 equivalents or less, preferably 0.1 equivalents or less, based on the equivalent of the terminal NCO group in (a).
[0021]
The method for producing the polyurethane resin (A) in the present invention may be a normal method and is not particularly limited.
(1) In the presence or absence of a hydrophilic organic solvent (for example, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, etc.) that does not contain an active hydrogen group in the molecule, (a), (b), and (e) if necessary Is usually reacted at 20 to 150 ° C., preferably 60 to 110 ° C. for 2 to 10 hours, to form a terminal NCO group-containing urethane prepolymer. The charge ratio of (a) :( b) in this reaction is calculated from the hydroxyl group equivalent of (a) and the NCO equivalent of (b), but is usually NCO / OH = 2/1 to 1.3 / 1. . The NCO content is usually 2.0 to 4.0%. Next, the prepolymer is usually used as a blocking agent (c-1) at 10 to 50 ° C., preferably at 20 to 40 ° C. for 1 to 2 hours in the presence of an emulsifier (g) comprising a nonionic surfactant as necessary. Specific examples include a method in which, after the blocking reaction, the mixture is usually emulsified by mixing with water at 10 to 60 ° C., preferably 20 to 40 ° C., and then the solvent is distilled off if necessary.
Examples of the emulsifier (g) comprising a nonionic surfactant as required include alkylene oxide addition type nonionic surfactant (g-1) and polyvalent alcohol type nonionic surfactant (g-2). Etc.
[0022]
As (g-1), polyoxyalkylene (alkylene group having 2 to 4 carbon atoms, the same applies to the following alkylene groups) alkyl (alkyl group having 8 to 18 carbon atoms) ether, polyoxyalkylene higher fatty acid (fatty acid) C8-20 ester, polyoxyalkylene polyvalent (2 to 8 valent) alcohol higher fatty acid (fatty acid carbon number 8 to 20) ester, polyvalent (2 to 8 valent) alcohol alkyl (carbon number of alkyl group) 1-18) ether alkylene oxide adduct, polyoxyalkylene alkyl or aralkyl (alkyl or aralkyl having 8 to 24 carbon atoms) phenyl ether, styrenated (1-7 mol) phenol polyoxyalkylene ether, polyoxyalkylene alkyl (alkyl) Group having 8 to 18 carbon atoms) amine and polyoxyalkylene (The number of carbon atoms in the alkyl group 8-18) kills such alkanolamides.
As (g-2), polyvalent (2 to 6 valent) alcohol fatty acid (fatty acid carbon number 8 to 20) ester, polyvalent (2 to 6 valent) alcohol alkyl (alkyl group carbon number 8 to 24) ether Etc.
Of these, polyoxyalkylene alkyl or aralkylphenyl ether and styrenated (1-7 mol) phenol polyoxyalkylene ether are preferred.
Examples of the alkylene oxide used in (g-1) or (g-2) include EO, PO, and 1,2-butylene oxide.
Of these, EO and random or block adducts of EO and PO are preferred.
The number of moles of alkylene oxide added is preferably 10 to 50 moles, and 50 to 100% by weight of the alkylene oxide is preferably EO. The HLB of (g) (HLB of Griffin) is usually 5 to 20, preferably 7 to 20.
[0023]
The production method of (A) further includes (2) in the presence or absence of a hydrophilic organic solvent (for example, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, etc.) that does not contain an active hydrogen group in the molecule (a) , (B), (d) and, if necessary, (e) are usually reacted at 20 to 150 ° C., preferably 60 to 110 ° C. for 2 to 10 hours by a one-stage method or a multi-stage method, and a terminal NCO group-containing urethane prepolymer. A polymer is formed. The charge ratio of (a) :( b) :( d) in this reaction is calculated from the average hydroxyl group equivalent of (a) and (d) and the NCO equivalent of (b), but usually NCO / OH = 2. / 1 to 1.3 / 1.
Next, the prepolymer is blocked at (c-2) (0.05 to 1.1 equivalents relative to the terminal NCO group) usually at 40 to 100 ° C., preferably at 50 to 100 ° C. for 1 to 3 hours, and then volatilized. And neutralizing with a basic base (for example, triethylamine), usually emulsifying by mixing with water at 10 to 60 ° C., preferably 20 to 40 ° C., and then distilling off the solvent.
[0024]
As the electrolyte (B) which is the other component in the present invention, the molar conductivity Λ at 25 ° C. of a 0.01 mol% aqueous solution is usually 110 to 130 S · cm.²・ Mole^-1, Preferably 110-120 S · cm²・ Mole^-1It is. Here, the symbol S is called siemens and is a unit of conductance representing the ease of charge flow and is one of the induction units of the international unit system (SI). In addition, the value of the molar conductivity of various compounds is described in 2-446-451 of the revised 4th edition "Chemical Handbook" basic edition 2 (edited by the Chemical Society of Japan: published in 1993). The molar conductivity is measured at 25 ± 0.2 ° C. using a conductivity meter “DS-15” (manufactured by Horiba, Ltd.) and using a platinum black plated conductivity electrode. You can also.
When the molar conductivity of the electrolyte is less than 100, the effect of preventing migration of the polyurethane resin when the fabric is treated is small, and when it exceeds 130, the polyurethane resin is deposited in the treatment aqueous solution or on the drawing roll such as mangle. There is.
The electrolyte (B) is an acid salt having an acid dissociation index pKa of 2.0 or less. The acid dissociation index pKa is a logarithmic value of the reciprocal of the dissociation constant of the electrolyte, and here refers to a value of 25 ° C. in an infinitely diluted aqueous solution. Specifically, it is described in 2-317 and 2-322 of the aforementioned revised 4th edition "Chemical Handbook". Examples of acids having a pKa of 2.00 or less include HCl: -8 and HNO.₃: -1.8, H₂SO₄: 1.99 (second stage dissociation), HBr: -9 and the like. When an electrolyte formed from an acid having a pKa of more than 2.0 is used, the effect of preventing migration of the polyurethane resin when the fabric is treated is small.
[0025]
Specific examples of the electrolyte (B) include the followings among those described in 2-446 to 451 of the revised 4th edition “Chemical Handbook”.
[0026]
For example, as an inorganic salt, the molar conductivity Λ is 110 to 130 S · cm.²・ Mole^-1And salts formed from strong acids and bases having a pKa of 2.0 or less include NaCl, NaI, NaBr, NaNO₃, Na₂SO₄, Na₂S₂O₃, K₂SO₄Etc. Of the inorganic salts, the molar conductivity Λ is 110 to 130 S · cm.²・ Mole^-1And a salt formed from a strong acid and a weak base having a pKa of 2.00 or less is Sr (NO₃)₂, Ba (NO₃)₂, Ca (NO₃)₂, CaCl₂, BaCl₂, AgNO₃, SrCl₂, CuCl₂, Cu (NO₃)₂MgCl₂, Mg (NO₃)₂, PbCl₂, Zn (NO₃)₂Etc. Examples of the organic compound include trimethylammonium chloride and 2-hydroxyethylammonium chloride. Of these, inorganic salts are preferable, and a salt (B1) formed from a strong acid and a strong base and (B1) and a salt (B2) formed from a strong acid and a weak base are more preferable. Particularly preferred is (B1). Among (B1), preferred is Na.₂SO₄And K₂SO₄It is. When (B1) and (B2) are used in combination, (B1) is preferably 50% or more, more preferably 80% or more, of the total weight of the inorganic salt. In the case of combined use, if (B1) is 50% or more, aggregates tend not to be generated in the treatment agent.
[0027]
The mixing ratio of (B) :( A) in the present invention is usually 0.5: 100 to 5.0: 100, preferably 1.0: 100 to 3: 100, based on the mass of (A). It is. When (B) is 0.5 or more, the migration prevention effect of the polyurethane resin is further improved, and when (B) is 5 or less, the polyurethane resin is less precipitated in the aqueous treatment solution or on the drawing roll such as mangle.
[0028]
The fiber treatment agent of the present invention may contain dibasic acid dihydrazide (C) as necessary. Examples of (C) include carbodihydrazide, hydrazide from C2-C8 aliphatic dibasic acid and hydrazine (glutaric acid dihydrazide, succinic dihydrazide, adipic acid dihydrazide, etc.), hydrazide from aromatic dibasic acid and hydrazine. (Isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc.). Of these, hydrazide from an aliphatic dibasic acid is preferable in terms of the texture of the treated fabric, and adipic acid dihydrazide is more preferable. In the present invention, the equivalent ratio of the (C) hydrazide group to the (A) blocked isocyanate group is usually (0.1 to 0.7): 1, preferably (0.2 to 0.5): 1. If the equivalent ratio of hydrazide groups is 0.1 or more, the water resistance is further improved, and if it is 0.7 or less, the texture of the treated cloth becomes more flexible.
[0029]
In the present invention, the mixing method of (A) and (B) and the mixing method further including (C) are not particularly limited. For example, an aqueous liquid containing (A) and an aqueous solution containing (B) and (C) Examples thereof include mixing by ordinary stirring and mixing using a mixing apparatus (such as a homomixer or a homodisper).
[0030]
If necessary, the fiber treatment agent of the present invention may contain a known antifoaming agent, wetting agent, various resin emulsions (polyurethane emulsions other than the present invention, acrylic emulsion, SBR latex, etc.), softeners, and the like. These compounding amounts are preferably 30% by mass or less, particularly preferably 20% by mass or less based on the mass of (A) in terms of solid content in the case of a resin emulsion, and 1% by mass or less in the case of other additives. In particular, it is preferably 0.1 to 0.5% by mass. Further, if necessary, a pH adjusting agent can be added. PH adjusters include alkaline substances such as salts of strong bases (alkali metals, etc.) and weak acids (acids with a pKa exceeding 2.0, such as carbonic acid, phosphoric acid, etc.) (sodium bicarbonate, etc.) or acidic substances (acetic acid, etc.) ). The amount of the pH adjusting agent is usually 0.01 to 0.3% by mass based on the mass of (A).
[0031]
The solid content (nonvolatile content) concentration of the fiber treatment agent of the present invention is not particularly limited, but is usually 10 to 50% by mass, preferably 15 to 45% by mass. Moreover, a viscosity (25 degreeC) is 10-1000 mPa * s normally.
[0032]
The fiber treatment agent of the present invention is applied to natural fibers such as wool, cotton and silk, regenerated fibers such as rayon and acetate, knitted fabrics such as synthetic fibers such as polyester, polyamide and polyacrylonitrile, and textile products such as woven fabrics and nonwoven fabrics. be able to. Among them, it is particularly suitably used as a treatment agent for imparting a soft texture and shrinkage resistance to natural fiber (especially wool) fabrics.
[0033]
As a method for applying the fiber treatment agent of the present invention to a textile product, the treatment agent is diluted with water to a required concentration (usually 1 to 5% by mass) to prepare a treatment agent diluted solution, followed by roll coating and immersion. After attaching to a textile product by a method such as dipping, etc., it is narrowed down to the required amount of attachment with mangles, pre-dried at 80 to 130 ° C. for 2 to 5 minutes, and further heat treated at 130 to 170 ° C. for 1 to 3 minutes can give.
The adhesion amount (non-volatile content) of (A) and (B) among the treatment agents for the fiber product is usually 1 to 5% by mass based on the mass of the fiber product before treatment. The mass ratio of (A) and (B) in the attached non-volatile content is the same as the mass ratio of (A) and (B) in the treatment agent.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following description, “part” means mass part, and “%” means mass%.
[0035]
Production Example 1
In a closed reaction vessel equipped with a thermometer and a stirrer, hydroxyl equivalent 1660 obtained by adding PO to glycerin, 124.3 parts of triol having 3 functional groups, 500 equivalents of hydroxyl group, 24.9 parts of polybutadiene glycol having 2 functional groups, and HDI 19 Then, 8 parts were charged and replaced with nitrogen gas, and reacted at 105 ° C. for 6 hours with stirring to obtain an NCO-terminated urethane prepolymer having a free isocyanate content (hereinafter referred to as NCO content) of 2.7%. The obtained urethane prepolymer was cooled to 30 ° C., and 17 parts of an emulsifier obtained by adding 19 moles of EO and 1.5 moles of PO to 1 mole of styrenated (2.75 mole) phenol, bisulfite. An aqueous sodium solution (11.1 parts of sodium bisulfite / 25.9 parts of water) and 82.5 parts of ethanol were added and mixed at 30 ° C. for 30 minutes to complete the reaction. To this, 736.8 parts of water and 3.4 parts of anhydrous magnesium chloride were added and mixed to obtain an aqueous ionic group-containing polyurethane resin dispersion having a solid content of 20% and a viscosity of 150 mPa · s. This aqueous dispersion of ionic group-containing polyurethane resin was diluted with water so that the solid content was 3%, and the pH was adjusted to 7 with sodium bicarbonate to obtain a treating agent diluted solution (Y1).
[0036]
Production Example 2
A treating agent diluent (Y2) was obtained in the same manner as in Production Example 1 except that polybutadiene glycol was replaced with polytetramethylene glycol having a hydroxyl group equivalent of 500 and a functional group number of 2.
[0037]
Production Example 3
A treating agent diluent (Y3) was obtained in the same manner as in Production Example 1 except that 3.4 parts of adipic acid dihydrazide was added after the block reaction in Production Example 1.
[0038]
Production Example 4
A treating agent diluent (Y4) was obtained in the same manner as in Production Example 1 except that anhydrous magnesium chloride was replaced with anhydrous sodium sulfate.
[0039]
Production Example 5
A treating agent diluent (Y5) was obtained in the same manner as in Production Example 2 except that anhydrous magnesium chloride was replaced with anhydrous potassium sulfate.
[0040]
Production Example 6
A treating agent diluent (Y5) was obtained in the same manner as in Production Example 2 except that 50% (1.7 parts) of anhydrous magnesium chloride was replaced with anhydrous sodium sulfate.
[0041]
Comparative production example 1
A comparative treatment agent diluted solution (Z1) was prepared in the same manner as in Production Example 1 except that anhydrous magnesium chloride was replaced with anhydrous potassium chloride.
[0042]
Comparative production example 2
A comparative treating agent diluent (Z2) was obtained in the same manner as in Production Example 1 except that anhydrous magnesium chloride was replaced with cuprous chloride.
[0043]
Comparative production example 3
A comparative treatment agent diluent (Z3) was obtained in the same manner as in Production Example 2 except that anhydrous magnesium chloride was replaced with potassium chloride.
[0044]
Comparative production example 4
A comparative treating agent diluent (Z4) was obtained in the same manner as in Production Example 4 except that anhydrous sodium sulfate was replaced with cuprous chloride.
[0045]
Examples 1-6 and Comparative Examples 1-4:
A performance test was performed by the following test method using the processing agent diluents (Y1 to Y6) and the comparative processing agent diluents (Z1 to Z4) obtained in Production Examples 1 to 6.
The test results are shown in Table 1.
[0046]
Performance Test Example 1 (Sedimentation stability test of treatment solution dilution)
The treating agent diluted solution was allowed to stand at room temperature (25 ° C.), and the time until the sediment was generated was measured. The symbols in Table 1 are: No sediment after 8 hours, o Precipitate generation in 4 to 8 hours, x Occurrence of sediment within 1 hour.
[0047]
Performance test example 2 (Bend stiffness test of treated cloth)
Unstained wool muslin for test (size: 25 cm × 25 m) was immersed in a diluent for treatment agent, and adjusted with a mangle so that the drawing rate was 90%. This immersion cloth was pre-dried at 100 ° C. for 3 minutes, and further heat-treated at 150 ° C. for 2 minutes to prepare a treated cloth.
Each treated cloth was cut into 20 cm × 20 cm and allowed to stand at 25 ° C. and 50% humidity for 3 hours, and then the bending stiffness of the treated cloth was measured with a KES pure bending tester.
[0048]
Performance Test Example 3 (Area shrinkage after washing of the treated fabric with detergent)
Each treated cloth obtained in the same manner as in Performance Test Example 3 was cut into 20 cm × 20 cm, washed under the following conditions, and the area shrinkage after 60 washes was measured.
Washing conditions: Household washing machine 2g / L, bath ratio 1/30, washing at 40 ° C warm water for 5 minutes, rinsing for 2 minutes, dehydration and 60 ° C horizontal after dehydration according to method 103 of JISL-0217-1976 Washing was repeated with one drying.
[0049]
[Table 1]

[0050]
【The invention's effect】
The fiber treatment agent of the present invention can give a soft texture and excellent shrinkage resistance to a textile product such as a woven fabric in a single treatment.
Because of the above effects, the fiber treatment agent of the present invention is made of natural fibers such as wool, cotton and silk, regenerated fibers such as rayon and acetate, woven fabrics, knitted fabrics and nonwoven fabrics such as synthetic fibers such as polyester, polyamide and polyacrylonitrile. It is useful as a finishing agent for textile products.

Claims (8)

An aqueous liquid containing a polyurethane resin (A) having an ionic group or / and an ion-forming group in the molecule and an electrolyte (B), wherein (A) contains an isocyanate group blocked with bisulfite Polyurethane resin having an acid dissociation index pKa of (B) 0.01 mol% aqueous solution at 25 ° C. having a molar conductivity Λ of 110 to 130 S · cm ² · mol ⁻¹ and (B) being 2.0 or less. A fiber treatment agent characterized by being a salt of an acid having the same. The fiber treatment agent according to claim 1, wherein (A) contains an ionic group or / and an ion-forming group at the end of the molecule. Ionic groups -SO ₃ ^- is, fiber treatment agent according to claim 1 or 2, wherein ion-forming group is an -SO ₃ H. The fiber treatment agent according to any one of claims 1 to 3, wherein (B) is a combination of a salt (B1) formed from a strong acid and a strong base (B1) or a salt (B2) formed from a strong acid and a weak base. . Furthermore, the fiber treatment agent in any one of Claims 1-4 containing dibasic acid dihydrazide (C). 6. (A) contains blocked isocyanate groups, and the equivalent ratio of (C) hydrazide groups to (A) blocked isocyanate groups is (0.1 to 0.7): 1. The fiber treatment agent as described. A finishing method for a textile product, wherein the fiber treatment agent according to any one of claims 1 to 6 is applied to the textile product and further heat-treated. A fiber product processed with the fiber treatment agent according to claim 1.