JPH0512472B2 - - Google Patents

Description

[Detailed description of the invention] [Purpose of the invention]

[Industrial Field of Application] The present invention relates to an improving agent and a method for improving the feel and color fastness of synthetic fibers, particularly polyester fibers, and products thereof. [Prior Art] (1) Background Synthetic fibers such as nylon and polyester, especially fabrics such as knitted fabrics, woven fabrics, and non-woven fabrics made of polyester fibers, especially when dyed with disperse dyes, have poor transfer sublimation fastness and abrasion fastness. For this reason, there has been a problem in the past that there are restrictions in terms of uses, types of dyes that can be applied, etc. On the other hand, resin processing is carried out to adjust the texture of these dyed fabrics and increase their added value.However, in these resin processing, the main purpose of these resin processing is to impart characteristic textures such as rebound resilience. Water-based polyurethane resin is used. (2) Problems with the conventional technology However, when the synthetic fibers, especially polyester synthetic fiber fabrics dyed with disperse dyes, are processed with the conventionally used aqueous polyurethane resin, the dyeing fastness is poor. The problem is that it either does not improve the strength at all, or in some cases even deteriorates it. [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a hand improver that can improve the color fastness of dyed fabrics made of the synthetic fibers, particularly polyester.

[Structure of the invention]

[Means for Solving the Problems] (1) Overview In order to achieve the above-mentioned object, the present invention provides a polyol in which hydrogen is added to the double bonds of polybutadiene polyol and a polyol in which hydrogen is added to the double bonds of polyisoprene polyol as a polyol component. The texture of dyed polyester fiber is characterized by using one or more polyolefin polyols selected from the group consisting of polyols, and containing as an active ingredient an aqueous polyurethane resin emulsified with a surfactant. The main topics are improvers and methods for improving texture. Hereinafter, various matters related to the structure of the invention will be explained in sections. (2) Polyolefin-based polyol The hand feel improver according to the present invention is characterized in that the aqueous polyurethane resin as its active ingredient specifically selects a polyolefin-based polyol as the polyol component. Examples of the polyolefin polyol used as a polyol component include, for example, a polyol obtained by adding hydrogen to the double bond of a polybutadiene polyol mainly consisting of 1,4 bonds,
A polyol consisting mainly of 1,2 bonds with hydrogen added to the double bonds of a polybutadiene polyol, a polyol consisting mainly of 1,4 bonds with hydrogen added to the double bonds of a polyisoprene polyol, a polyisoprene consisting mainly of 1,2 bonds. Examples include polyols with a high degree of saturation, such as polyols in which hydrogen is added to the double bonds of polyols. The polyolefin polyol preferably has an average molecular weight of 500 to 5,000 and an average functional number of hydroxyl groups of 1.5 to 3.0. In the present invention agent, in addition to the above-mentioned polyolefin polyols, a polyol compound containing two or more hydroxyl groups, which is commonly used in the production of urethane resins, can be used in combination, if desired. Examples of such polyol compounds containing two or more hydroxyl groups include polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, diethylene glycol, trimethylolpropane, glycerin, and methylpentanediol. , adducts (random or block) obtained by adding one or more alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide to the above polyhydric alcohols, polyoxytetramethylene glycol which is a ring-opening polymer of tetrahydrofuran. are condensation products of the polyhydric alcohols and polyhydric saturated or unsaturated carboxylic acids such as succinic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, or their acid anhydrides. There are polyester polyols. When the above-mentioned polyols commonly used in the production of urethane resins are used together, the blending ratio of the polyols to the polyolefin polyol is desirably within 60% by weight, preferably within 40% by weight. If the content of the polyolefin polyol in the composition is less than 40% by weight, it will not be possible to impart the excellent color fastness, which is a feature of the present invention, to the treated polyester fiber fabric dyed with a disperse dye. The term "olefin polyol" used herein refers to -C=C- of polyolefin polyols and polydiofin polyols.
It means a highly saturated or saturated linear hydrocarbon polyol in which hydrogen is added to most or all of the double bonds. (3) Polyisocyanate compound Examples of the polyisocyanate component, that is, the polyisocyanate compound used to prepare the aqueous polyurethane resin of the present invention, include tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate,
Conventionally known polyisocyanate compounds such as xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), hexamethylene diisocyanate (HMDI), and tetramethylxylylene diisocyanate (TMXDI) can be mentioned, but for clothing. When considering the usage, XDI with low yellowing or non-yellowing type,
IPDI, H12MDI, TMXDI, etc. are preferred. (4) Preparation of water-based polyurethane resin The method for producing the water-based polyurethane resin according to the present invention is obtained by reacting a polyol and a polyisocyanate compound in the presence or absence of an inert organic solvent that does not react with isocyanate groups. After producing a urethane prepolymer containing free isocyanate groups at the terminals, this urethane prepolymer is converted into a nonionic,
A method of mechanically emulsifying and dispersing in water using one or more surfactants such as anionic or cationic surfactants: Alternatively, the urethane prepolymer containing a free isocyanate group at the end is converted into isocyanate by heat treatment. Blocking with known blocking agents that regenerate groups, such as phenols or alkylphenols or oximes such as butanone oxime, lactams such as caprolactam, imides such as succinimide, imidazoles such as imidazole or alkylimidazole, etc. Then, the urethane prepolymer is mechanically emulsified and dispersed in water using the surfactant; or the urethane prepolymer is blocked with acidic sulfates and made aqueous using a nonionic or anionic surfactant. Examples include methods. Note that, if desired, the solvent used in the reaction may be finally distilled off under reduced pressure. (5) Fibers The hand feel improver of the present invention is particularly effective for dyed polyester synthetic fibers. (6) Usage The aqueous polyurethane resin synthesized using a polyolefin polyol as the polyol component according to the present invention can be used in dyed fabrics such as knitted fabrics, woven fabrics, and nonwoven fabrics made of synthetic fibers such as polyester;
In particular, it is applied by impregnation or coating to dyed fabrics made of polyester fibers dyed with disperse dyes, which fabrics are then heated at e.g.
heat treated. In this case, fillers, thickeners, softeners, etc. may be used in combination, if necessary. [Function] The dyed fabric made of polyester synthetic fiber texture-treated using the texture improver (aqueous polyurethane resin) according to the present invention has only excellent color fastness such as transfer sublimation fastness and rubbing fastness. It has a distinctive texture that also has anti-bacterial properties. Although it is not possible to fully explain the reason why the color fastness is improved by the aqueous polyurethane resin of the present invention, it is likely that the aqueous polyurethane resin of the present invention has poor affinity with dyes, especially for dyeing polyester fibers. One of the reasons may be that poor affinity with the disperse dye used acts to prevent migration of the disperse dye. [Examples] The details and effects of the invention will be described below using Examples and Comparative Examples, but the examples are merely for explanation and are not intended to limit the idea of the invention. Note that parts and % in the description mean parts by weight and % by weight, respectively. Synthesis Example 1 Hydroxyl value 50.0 obtained by adding hydrogen to a polybutadiene polyol mainly consisting of 1,4 bonds
(KOHmg/g) of polyol (saturation level of 99% or more,
180 parts of polyoxyethylene/propylene random copolymer glycol (average molecular weight: 3400, oxyethylene content: 80)
%) 12.0 parts, polyoxyethylene glycol 12.0
parts (average molecular weight 600), trimethylolpropane
6.70 parts, 3-methyl-1,5-pentanediol
Add 33.0 parts and 259 parts of methyl ethyl ketone, and add tetramethyl xylylene diisocyanate while stirring.
126 parts of dibutyltin dilaurate were added followed by 0.04 parts of dibutyltin dilaurate and the reaction was carried out at 75° C. for 80 minutes to obtain a methyl ethyl ketone solution of the urethane prepolymer containing 0.50% of free isocyanate groups. To this solution, 38 parts of a nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of alkylphenol, was added, and after mixing, it was mixed with water at room temperature.
After adding 500 parts, stirring and emulsifying with a homomixer, methyl ethyl ketone was distilled off at 40 to 50°C under reduced pressure with an evaporator to obtain a milky white aqueous polyurethane resin emulsion with a solid content of 46%. Synthesis Example 2 Hydroxyl value 53.0 obtained by adding hydrogen to polyisoprene polyol mainly consisting of 1,4 bonds
(KOHmg/g) of polyol (saturation level of 99% or more,
Number of functional groups: 2.0 Average molecular weight: 2100) 180 parts, Synthesis Example 1
14.0 parts of polyoxyethylene/propylene random copolymerized glycol similar to that used in , 14.0 parts of polyoxyethylene glycol, 3-methyl-1,
After adding 40 parts of 5-pentanediol and 8.0 parts of trimethylolpropane, 370 parts of methyl ethyl ketone was added, followed by hexamethylene diisocyanate.
After adding 144 parts, 0.05 part of dibutyltin dilaurate was added with stirring, and the mixture was reacted at 75°C for 160 minutes.
A methyl ethyl ketone solution of a urethane prepolymer containing 1.0% of free isocyanate groups was obtained. To this solution, add 50 parts of a nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of alkylphenol, and mix.
After adding 1270 parts and emulsifying the mixture, methyl ethyl ketone was distilled off in the same manner as in Example 1 to obtain a milky white aqueous polyurethane resin emulsion with a solid content of 35%. Synthesis Example 3 In Synthesis Example 2, 11.5 parts of butanone oxime was added to 500 parts of a methyl ethyl ketone solution of the partially reacted urethane prepolymer containing 1.0% free isocyanate groups, and the reaction was carried out at 50°C for 80 minutes to eliminate the free isocyanate groups. After confirming that the
After stirring, 475 parts of water at room temperature was added and emulsified in the same manner. After stirring for 60 minutes, methyl ethyl ketone was distilled off in the same manner as in Synthesis Example 1, and the solid content 3
%, a milky white aqueous polyurethane resin emulsion was obtained. Comparative synthesis example 1 Polybutylene adipate diol (average molecular weight
2000) 180 parts, polyethylene/propylene random copolymer glycol (average molecular weight 3400, oxyethylene content 80%) 12.0 parts, polyoxyethylene glycol (average molecular weight = 600) 12 parts, trimethylolpropane 6.70 parts, 3-methyl- 1,5-
33.0 parts of pentanediol and methyl ethyl ketone
259 parts of the mixture were added, and while stirring, 126 parts of tetramethylxylylene diisocyanate and 0.08 parts of dibucytyltin dilaurate were successively added, and the mixture was reacted at 75°C for 120 minutes. A solution of urethane prepolymer in methyl ethyl ketone containing 0.48% of free isocyanate groups was obtained. To this solution, 38 parts of a nonionic surfactant (HLB = 15), which is an ethylene oxide adduct of alkylphenol, was added and mixed.
570 parts were added and emulsified in the usual manner, and methyl ethyl ketone was distilled off using an evaporator in the same manner as in Synthesis Example 1 to obtain a milky white aqueous polyurethane resin emulsion with a solid content of 45%. Comparative Synthesis Example 2 In Comparative Synthesis Example 1, 5.5 parts of butanone oxime was added to 500 parts of a methyl ethyl ketone solution of a partially reacted urethane prepolymer containing 0.48% free isocyanate groups, and the mixture was reacted at 50°C for 80 minutes to form free isocyanate groups. After confirming that the
After stirring, 400 parts of room temperature water was added and emulsified in a conventional manner. Thereafter, stirring was continued for another 60 minutes, and methyl ethyl ketone was distilled off using an evaporator in the same manner as in Synthesis Example 1 to obtain a milky white aqueous polyurethane resin emulsion with a solid content of 44%. Usage Example 1 The aqueous polyurethane resin emulsions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 above were diluted with water to a solid content of 3%, and each was impregnated into a dyed polyester cloth, After squeezing with a mangle to achieve a squeezing rate of 80%, pre-dry at 120℃ for 1 minute.
Heat treatment was performed at 150°C for 1 minute. after that,
The dry and wet rubbing fastness of each resin-treated dyed fabric
Based on JIS L 0849, measurements were made according to the standards shown in Table 1 below, and the results shown in Table 2 below were obtained. Note that the measurement results for untreated dyed fabric are shown as blanks.

【table】

[Table] As can be seen from Table 2 above, the fabric samples treated with the aqueous polyurethane resin emulsions of Synthesis Examples 1 to 3 according to the present invention exhibited excellent hand feel and excellent abrasion fastness. known. Example 2 An acrylic acid thickener was added to the aqueous polyurethane resin emulsions obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 to prepare coating liquid samples each having a thickness of about 1000 centipoise. Next, each coating solution was applied with a roll coater to a dyed polyester knit cloth (color: red) that had been pre-water-repellent treated with a 0.2% aqueous solution of fluorine emulsion, pre-dried at 120°C for 2 minutes, and heat-treated for 150°C. Heat treated under the conditions of ℃ x 3 minutes to reduce the solid content of each
A coated fabric was prepared at a rate of 40 g/m ² . Separately, a polyester knit white cloth was coated and heat treated in the same manner as above. Next, each coated dyed fabric and each coated white fabric coated with the same coating solution are pasted together so that the coated surfaces face inward, and the specified load specified in JIS L 0822 is applied. was added and treated under the conditions shown in Table 3 below.

[Table] Thereafter, the test fabrics were peeled off from each other, and the sublimation fastness (degree of staining) of the coated surface of the white fabric was evaluated according to the evaluation criteria in Table 4 below. The results are shown in Table 5 below. Note that the sublimation fastness of untreated fabric is shown as a blank.

【table】

【table】

[Table] As shown in Table 5 above, it was confirmed that the fabric treated with the aqueous polyurethane resin emulsion according to the present invention had excellent sublimation fastness and a soft texture.

【Effect of the invention】

As explained and demonstrated above, the present invention can contribute to the development of the textile industry by providing a hand improver that can improve the color fastness of polyester fabrics dyed with disperse dyes.

Claims (1)

[Scope of Claims] 1. One or more polyolefins selected from the group consisting of a polyol with hydrogen added to the double bond of polybutadiene polyol and a polyol with hydrogen added to the double bond of polyisoprene polyol as a polyol component. A hand-improving agent for dyed polyester fibers, which uses a polyol-based polyol and contains as an active ingredient an aqueous polyurethane resin emulsified with a surfactant. 2. A method for improving the texture of dyed polyester fibers, which comprises using the improving agent according to claim 1.