WO2012091504A2

WO2012091504A2 - Polyurethane elastic fiber and method for manufacturing same

Info

Publication number: WO2012091504A2
Application number: PCT/KR2011/010343
Authority: WO
Inventors: 정호영; 강연수
Original assignee: 주식회사 효성
Priority date: 2010-12-31
Filing date: 2011-12-29
Publication date: 2012-07-05
Also published as: WO2012091504A3; KR20120089959A; KR101247888B1

Abstract

Provided is a method for manufacturing an eco-friendly polyurethane elastic fiber which is harmless to the human body, by providing a method for manufacturing a polyurethane elastic fiber, which does not use an organic solvent, according to a process of dry-weaving of an aqueous, ionic, and hydrophilic polyurethane dispersion liquid.

Description

Polyurethane elastic yarn and its manufacturing method

The present invention relates to a method for producing a polyurethane elastic yarn that is environmentally friendly and harmless to the human body.

Elastic fibers are widely used in stretch fabric materials or industrial materials such as legwear, innerwear, sportswear, etc. because of their excellent stretch properties.

Among these elastic fibers, in particular, polyurethane elastic yarns are used in combination with various materials, such as nylon or polyester yarns, as well as natural fibers such as cotton or wool, semisynthetic fibers, and the like.

In the production of polyurethane elastic yarns, a method of dissolving a polymer using an organic solvent and then drying the organic solvent at a high temperature has generally been used. However, there may be a problem that the organic solvent is released into the atmosphere, or a certain amount of the elastic yarn produced to be harmful to the environment or human body.

The present invention has been made to solve the above problems, to provide a polyurethane elastic yarn that is environmentally friendly and safe to human body by not using an organic solvent in the manufacturing process.

Method for producing a polyurethane elastic yarn according to the invention, the step of preparing a first prepolymer by reacting a polyisocyanate, ester or ester-based polyol; Reacting an isocyanate with a bifunctional or polyfunctional alcohol comprising —COOH or —SO ₃ H, to prepare a second prepolymer; Preparing a third prepolymer by chain-extending the reaction product of the first prepolymer and the second prepolymer; And neutralizing the third prepolymer to prepare a dispersion.

According to the production method of the present invention, it is possible to obtain a polyurethane elastic yarn that is environmentally friendly and safe for human body by not using an organic solvent in the manufacturing process.

The present invention provides a method for producing a polyurethane elastic yarn without using a conventional organic solvent. In particular, by forming an aqueous ionic block urethane group, an elastic ionic hydrophilic polyurethane dispersion is prepared and a polyurethane elastic yarn is produced by drying it by a dry process.

Method for producing a polyurethane elastic yarn according to an embodiment of the present invention, the step of preparing a first prepolymer by reacting a polyisocyanate, ester or ester-based polyol; Reacting an isocyanate with a bifunctional or polyfunctional alcohol comprising —COOH or —SO ₃ H, to prepare a second prepolymer; Preparing a third prepolymer by chain-extending the reaction product of the first prepolymer and the second prepolymer; And neutralizing the third prepolymer to prepare a dispersion.

As the isocyanate used in the preparation of the prepolymer, aromatic, aliphatic and alicyclic diisocyanates or mixtures thereof may be used. For example, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, meta-phenylene diisocyanate, biphenylene-4,4'- diisocyanate, methylenebis ((4-phenyl Isocyanate), 4-chloro-1,3-phenylene diisocyanate, naphthalene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, decamethylene-1, 10-diisocyanate, cyclohexylene-1,4-diisocyanate, methylenebis (4-cyclohexyl isocyanate), tetrahydronaphthylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) Or those selected from the group consisting of two or more of these mixtures may be used. Preferably isophorone diisocyanate, hexamethylene-1,6-diisocyanate, cyclohexylene-1,4-diisocyanate, 4 , 4'-methylenebis (cyclohexyl isocyanate) and the like can be used.

Examples of the polyol used to prepare the prepolymer include polyester polyols and polyether polyols. Suitable polyester polyols are preferably obtained by condensation of a dicarboxylic acid compound with a diol compound, wherein the dicarboxylic acid compound is succinic acid, glutaric acid, adipic acid, subberic acid, azelanic acid. , Sebacic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, isophthalic acid, terephthalic acid, ortho-phthalic acid, tetrachlorophthalic acid, 1,5-naphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid And tetrahydrophthalic acid. Examples of the diol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1.5-pentanediol, and 1,6-hexane. Diol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, dibutylene glycol, 2-methyl-1,3-pentanediol, 2,2,4-trimethyl-1,3- Pentanediol, 1,4-cyclohexanedimethane Or all. Suitable polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. The molecular weight of the polyols varies from 400 to 10,000, but the suitable molecular weight is about 400 to 3,000. In addition, the polyol used in the present invention may be at least one selected from the group consisting of ether polyols such as polytetramethylene ether glycol, polypropylene glycol, and the like. The molecular weight of the polyol used in the present invention may be about 500 to 4000.

Anionic chain extenders and cationic chain extenders may be used as the ionic chain extender for self-emulsifying the prepolymer, and as the anionic chain extender, a compound including a carboxyl group or a sulfonate group may be used. , 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, polypropylene glycol with sodium sulfonate group, 2,4-diamino-5-methylbenzenesulfonic acid and the like can be used. As the cationic chain extender, tertiary amine diols and diamine compounds, for example, methyl diethanolamine may be used. The ionic chain extender may include 0.5 to 25% by weight, preferably 2 to 7% by weight based on the total polyurethane. Neutralizing agents are used to convert the ionic groups into salts in order to enable the dispersion of the anionic or cationic groups covalently bonded in the main chain of the polyurethane for self-emulsification. Such neutralizing agents include, when anionic, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, trimethylamine, triethylamine, triisopropylamine, tributylamine, N, N-dimethylcyclohexylamine, N, N-dimethylaniline , N-methylmorpholine, N-methylpiperazine, N-methylpyrrolidine, N-methylpiperidine, and the like, and in the case of cationic acid, phosphoric acid, hydrochloric acid, acetic acid, formic acid, malic acid Will be used. It can be used more than 80% stoichiometrically with respect to the ionic group. The isocyanate and polyol are reacted at a ratio of 1.1: 1 to 4.0: 1 to form polyisocyanate.

The prepolymer may be further polymerized by reaction with a chain extender after it is dispersed in water. As the chain extender, at least one selected from the group consisting of polyamines and lower alcohols may be used. Examples of the polyamine include hydrazine, ethylenediamine, piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N, N, N-tris (2-aminoethyl) amine, N- (2-piperazinoethyl) ethylenediamine, N, N'-bis (2-aminoethyl) piperazine, N, N, N'-tris (2-aminoethyl) ethylenediamine, N- [N- (2 -Aminoethyl) -2-aminoethyl] -N '-(2-aminoethyl) piperazine, N- (2-aminoethyl) -N'-(2-piperazinoethyl) ethylenediamine, N, N- Bis (2-aminoethyl) -N- (2-piperazinoethyl) amine, N, N-bis (2-piperazinoethyl) amine, guanidine, melamine, N- (2-aminoethyl) -1, 3-propanediamine, 3,3'-diaminobenzidine, 2,4,6-triaminopyrimidine, dipropylenetriamine, tetrapropylenepentamine, tripropylenetetramine, N, N-bis (6-aminohexyl ) Amine, N, N'-bis (3-aminopropyl) ethylenediamine, 2,4-bis (4'-aminobenzyl) aniline, 1,4-part Tandiamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 2-methylpentamethylenediamine, 1,12-dodecanediamine, isophoronediamine (or 1-amino-3- Aminomethyl-3,5,5-trimethyl-cyclohexane), bis (4-aminocyclohexyl) methane (or bis (aminocyclohexane-4-yl) -methane) and the like. Lower alcohols used at this time include ethylene glycol (EG), propylene glycol (Propylene Glycol: PG), diethylene glycol (Diethylene Glycol: DEG), dipropylene glycol (DPG), butylene glycol (Butylene) Glycol: 1,4BD)).

The dispersion is an aqueous ionic hydrophilic polyurethane dispersion, by adding a viscosity modifier to the dispersion to adjust the viscosity, by performing a dry spinning process using the dispersion can be produced an environmentally friendly and harmless polyurethane elastic yarn. .

Polyurethane elastic yarn produced by the above method can be used as it is, or covered with polyamide fibers and the like can be suitably used in thin knitted fabrics such as stockings, tights, socks.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

The first prepolymer was prepared by reacting 4,4'-methylene diphenyl diisocyanate with polytetramethylene ether glycol (molecular weight 1800). A second prepolymer was prepared using 2,2-dimethylolpropionic acid and 4,4'-methylene diphenyl diisocyanate. The first prepolymer and the second prepolymer were reacted, and a third prepolymer was prepared using ethylenediamine (EDA) as a chain extender. After neutralizing the third prepolymer for 2 hours by adding triethylenetetramine, a dispersion was prepared while adding deionized water, and the dispersion was added with a thickening agent BYK ® -428 to 250 cps. It was adjusted to (40 ℃), and the 20 denier polyurethane elastic yarn was prepared through a dry process using the dispersion. And the physical properties were evaluated and shown in Table 1.

Example 2

Instead of 4,4'-methylene diphenyl diisocyanate, using a 50:50 mixture of 4,4'-methylene diphenyl diisocyanate and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), the viscosity of the dispersion Polyurethane elastic yarn was manufactured in the same manner as in Example 1, except that it was adjusted to 110 cps (40 ° C.). And the physical properties were evaluated and shown in Table 1.

Example 3

Using a 50:50 mixture of 4,4'-methylene diphenyl diisocyanate and isophorone diisocyanate (IPDI) instead of 4,4'-methylene diphenyl diisocyanate, using 1,4-butanediol as chain extender , The polyurethane elastic yarn was manufactured in the same manner as in Example 1 except that the viscosity of the dispersion was adjusted to 180 cps (40 ° C.). And the physical properties were evaluated and shown in Table 1.

Comparative Example 1

As a capping ratio (CR) of 1.55 and polyol, polytetramethylene ether glycol (molecular weight 1800) was used, and 4,4'-diphenylmethane diisocyanate was mixed and prepared. Ethylenediamine was used as the chain extender and diethylamine was used as the chain terminator. The ratio of the chain extender to the chain terminator was 10: 1, and the amine used was prepared at a total concentration of 7 mol%, and dimethylacetamide was used as a solvent to obtain a polyurethaneurea spinning stock solution. The spinning stock solution obtained as described above was prepared in a polyurethane elastic yarn through a dry spinning process, and the physical properties thereof are shown in Table 1 below.

Tensile Strength and Elongation Measurement

Using an automatic elongation measuring device (MEL machine, Textechno Co., Ltd.), measure the sample length as 10cm and tensile speed 100cm / min. At this time, the strength and elongation at break are measured, and the load on the yarn (200% modulus) at 200% elongation of the yarn is also measured.

In Examples 1 to 4 and Comparative Example 1, the results of measuring physical properties such as dispersion viscosity, particle size, strength and elongation at a specific winding speed of the polyurethane elastic yarn are shown in Table 1 below.

Table 1

division	Example 1	Example 2	Example 3	Comparative Example 1
Isocyanate	4,4-MDI 100%	4,4-MDI 50% H12MDI 50%	4,4-MDI 50% IPDI 50%	4,4-MDI 100%
Polyol	PTMG	PTMG	PTMG	PTMG
Chain extender	EDA	EDA	1,4-Butandiol	EDA
Dispersion Viscosity (CPS @ 40 ℃)	250	110	180	-
Particle size	<60	<40	<100	-
Winding speed (m / min)	150	150	150	850
Strength (g / De)	12.5	10.5	7.5	1.1
Elongation (%)	250	340	410	520

Referring to Table 1, it was possible to produce an environmentally friendly elastic yarn showing a similar level of physical properties by varying various isocyanates compared to the elastic yarn prepared using the conventional organic solvent of Comparative Example 1.

Claims

Reacting the polyisocyanate with an ester or ester polyol to prepare a first prepolymer;

Reacting an isocyanate with a bifunctional or polyfunctional alcohol comprising —COOH or —SO 3 H, to prepare a second prepolymer;

Preparing a third prepolymer by chain-extending the reaction product of the first prepolymer and the second prepolymer; And

Neutralizing the third prepolymer, thereby preparing a dispersion.
The method of claim 1,

The polyisocyanate is 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1, At least one selected from the group consisting of 4'-cyclohexane diisocyanate, 4,4'- dicyclohexyl methane diisocyanate, or isophorone diisocyanate.
The method of claim 1,

The polyol is at least one selected from the group consisting of polyol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol obtained by the condensation reaction of a dicarboxylic acid compound and a diol compound, the production of polyurethane elastic yarn Way.
The method of claim 1,

In the chain extension reaction, at least one selected from the group consisting of polyamines and lower alcohols is used as a chain extender, and as the polyamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1, At least one lower alcohol selected from the group consisting of 4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclochlorodiamine Ethylene Glycol (EG), Propylene Glycol (PG), Diethylene Glycol (DEG), Dipropylene Glycol (DPG) and Butylene Glycol (1,4BD) At least one selected from the group consisting of, Polyurethane elastic yarn manufacturing method.
The method of claim 1,

The dispersion is a method of producing a polyurethane elastic yarn, characterized in that the aqueous ionic hydrophilic polyurethane dispersion.
The method of claim 1,

Method for producing a polyurethane elastic yarn, characterized in that further adding a viscosity modifier to the dispersion.
The method of claim 1,

Method for producing a polyurethane elastic yarn, characterized in that to perform a dry spinning process using the dispersion.
Polyurethane elastic yarn produced by the method of any one of claims 1 to 7.