KR20200024053A - Elastic fiber having improved dying property - Google Patents

Abstract

The present invention relates to a polyurethane urea elastic yarn having improved dyeing properties of 0.5 times or more compared to a relative yarn. The polyurethane urea elastic yarn comprises: (a) polyol; (b) one or more diisocyanates; (c) one or more diamine chain extenders; and (d) a product of reacting one or more amine chain terminators.

Description

Elastic fiber having improved dying property

The present invention relates to a polyurethaneurea elastic yarn with improved dyeability, and more particularly, to a polyurethaneurea elastic yarn that solves the problem of low dyeability compared to the counterpart yarns when the polyurethaneurea elastic yarn is knitted with a counterpart yarn such as nylon and cotton. .

Polyurethane fibers having elastic properties are widely used in the textile industry. 'Spandex' fiber is used as a general term for such an elastic fiber, and usually refers to a synthetic fiber having a polyurethane bond of 85% or more of the structure forming the fiber.

Such polyurethane fibers generally react with a polyol which is a high molecular weight diol compound and an excess of diisocyanate compound to obtain a prepolymer having an isocyanate group at both ends of the polyol and the prepolymer in an appropriate solvent. After dissolution, the solution is prepared by a secondary polymerization reaction in which a diamine-based or diol-based chain extender is added and reacted.

Polyurethane fibers may be used in combination with various other fibers such as acrylic, wool, cotton, silk, etc., depending on the application, and have been commonly used for the purpose of requiring elasticity such as underwear, swimwear, and stockings.

Due to the inherent characteristics of such elasticity, polyurethane fibers are actively used for various purposes, and as the use thereof is expanded, new additional properties are continuously required for existing polyurethane fibers. Until now, a number of polyurethane fibers, which have been further strengthened in heat resistance and elastic recovery, have been developed, and in recent years, there is an increasing demand for polyurethane fibers having high heat setability and polyurethane fibers having improved dyeability.

Polyurethane fibers generally have a problem of poor dyeing, and a general technique for improving dyeing of acid dyes is 1) a method of introducing a tertiary nitrogen atom into a polyurethane polymer chain (Japanese Patent Publication No. 62 -23097), 2) A method of introducing a salt of an organic or inorganic acid and a tertiary amine into a polyurethane polymer chain (Japanese Patent Publication No. 50-17520), 3) A tertiary or A method of introducing a quaternary nitrogen atom (Japanese Patent Publication No. 44-16386), and 4) a method of using a low molecular diamine as a chain extender (Japanese Patent Publication No. 59-108021).

However, Method 1) and Method 2) tend to become gels during the reaction, and Method 3) has a problem that it is difficult to control the amount of nitrogen atoms introduced. In addition, method 4) using a low molecular weight diamine as a chain extender may improve dyeing property, but has a problem of lowering softness and elasticity.

In addition, Korean Patent Publication Nos. 10-2009-0118997 and 10-2005-0070652 disclose dyeing properties by dyeing with a specific blue acid dye containing a polymer having a maleimide structure composed of maleimide units or by adding a talc compound. To improve, but there was a limit to sufficiently improve the dyeability of the polyurethane.

The present invention has a problem that the polyurethane fiber generally has a problem that the dyeability is not good, and to solve the problem that the grin through phenomenon occurs on the fabric because the dye absorption rate is lower than the counterpart yarn, the dyeability of the polyurethane urea elastic yarn The problem is to provide a polyurethane urea elastic yarn with improved dyeability on the fabric by improving the dye absorption rate compared to the counterpart yarn.

As a means for solving the above problem,

Polyurethane urea elastic yarn improved dyeability of the present invention, (a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a polyurethaneurea elastic yarn comprising a product of reacting at least one amine chain terminator, wherein the second polyol is polyethylene glycol, and the first polyol and the second polyol are different materials from each other It is characterized by the fact that the removal rate is 0.5 times or more.

In addition, the polyethylene glycol is characterized by mixing 5.0 to 30.0 mol% relative to the total polyol.

In addition, the number of terminal amines of the polyurethane urea elastic yarn is characterized in that the terminal number is 20.0 to 45.0 meq / kg.

In addition, the counterpart is characterized in that the nylon or cotton.

In addition, the dye is characterized in that the acid dye or reactive dye.

The present invention can obtain a polyurethane urea elastic yarn with improved dyeability to the dye, and furthermore, even in the fabric knitted with the other yarns, such as nylon, cotton, there is an effect that can be expected to be uniform dyeing of deep colors.

Hereinafter, the polyurethaneurea elastic yarn with improved dyeability of the present invention will be described in more detail.

The present invention (a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a polyurethaneurea elastic yarn comprising a product obtained by reacting at least one amine chain terminator, wherein the second polyol is polyethylene glycol, and the first polyol and the second polyol are different materials, The present invention relates to a polyurethaneurea elastic yarn having improved stainability of 0.5 times or more.

In the present invention, the polyol includes a first polyol and a second polyol. That is, the first polyol and the second polyol are mixed and used as a polyol, and the first polyol and the second polyol are different materials.

In the present invention, the first polyol may be polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like.

In the present invention, the second polyol is polyethylene glycol. Polyethyleneglycol has excellent hydrophilicity, so that the mixed application at the stage of preparing the polyurethane prepolymer improves the hydrophilicity of the polyurethaneurea elastic yarn, thereby improving the accessibility of the acidic dye to the polyurethaneurea elastic yarn, and The dyeability of polyurethaneurea elastic yarn can be improved.

In the present invention, the polyethylene glycol is preferably mixed 5.0 to 30.0 mol% relative to the total polyol. When the polyethylene glycol is applied at less than 5.0 mol%, it is not expected to improve the dyeability, and when applied at more than 30.0 mol% may cause serious degradation of the elastic properties and process applicability.

In the present invention, as the diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, butylene diisocyanate, hydrogenated P, P-methylene diisocyanate and the like can be used. The above can be used.

The polyol and diisocyanate are contacted to prepare a polyurethane prepolymer, to which a solvent is added. At this time, the solvent is preferably dimethylacetamide. Thereafter, the polyurethaneurea solution is prepared by contact with at least one chain extender and at least one chain terminator. Polyurethane urea elastic yarn is prepared through a fiber spinning process such as dry spinning or melt spinning of the prepared product polyurethaneurea solution.

In the present invention, the chain extender is at least one diamine. Examples of diamines that can be used include hydrazine, ethylene diamine, 1,2-propanediamine, 1,3-propanediamine, 1,2-butanediamine (1,2-diaminobutane), 1,3-butanediamine (1,3 -Diaminobutane), 1,4-butanediamine (1,4-diaminobutane), 1,3-diamino-2,2-dimethylbutane, 4,4'-methylenebis-cyclohexylamine, 1- Amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 1,6-hexanediamine, 2,2-dimethyl-1,3-diaminopropane, 2,4-diamino-1-methylcyclohexane , N-methylaminobis (3-propylamine), 2-methyl-1,5-pentanediamine, 1,5-diaminopentane, 1,4-cyclohexanediamine, 1,3-diamino-4-methyl Cyclohexane, 1,3-cyclohexane-diamine, 1,1-methylene-bis (4,4'-diaminohexane), 3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-pentane Diamine (1,3-diaminopentane), m-xylylenediamine, and mixtures thereof, but is not limited thereto. Ethylenediamine is preferred as the chain extender.

In the present invention, the chain terminator is at least one amine. Examples of the amines that can be used include, but are not limited to, diethylamine, cyclohexylamine, n-hexylamine and mixtures thereof. Diethylamine is preferred as chain terminator.

It is preferable that the polyurethane urea elastic yarn of this invention is 20.0-45.0 meq / kg of amine terminal number of yarns. The amine end of the yarn serves as a dyeing seat bondable with the dye. When the number of amine ends of the yarn is less than 20.0 meq / kg, insufficient dyeing improvement effect cannot be expected due to the lack of the dyeing seat. In addition, when the number of amine end of the yarn is more than 45.0 meq / kg, the dyeability is sufficient, but excessive increase in the number of amine end may cause a big problem in the storage stability of the polymer.

In addition, in the present invention, in order to prevent discoloration of the polyurethane urea and deterioration of physical properties due to ultraviolet rays, atmospheric smog and heat treatment process associated with spandex processing, a steric hindrance phenol compound, a benzofuran-one compound, and a semicarbazide Type compound, a benzo triazole type compound, a polymeric tertiary amine stabilizer, etc. can be added combining them suitably. In addition to the above components, the spandex fiber of the present invention may be added with a pigment or dye showing a blue complementary color of yellow to alleviate yellowish yarn.

Furthermore, the polyurethaneurea elastic yarn of the present invention may include additives such as titanium dioxide, magnesium stearate, and the like in addition to the above components.

Polyurethane urea elastic yarn of the present invention can produce a fabric by knitting with nylon, PET, cotton, etc. as a counterpart yarns, in the case of such a knitted fabric is improved dyeing is excellent dyeing deep color effect of the fabric.

It is preferable that the polyurethane urea elastic yarn of the present invention has a dye absorption rate of 0.5 times or more relative to the counterpart yarn. If the dye absorption rate is less than 0.5 times compared to the counterparts, it is difficult to expect deep dyeing of the fabric due to a slight improvement in dyeability.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, and these examples are only to illustrate the present invention and should not be construed as limiting the scope of the present invention.

The measuring method for the properties of the elastic yarn shown in Examples and Comparative Examples to be described later is as follows.

(1) 200% M measurement method

It measures by using load cell 32cN, sample length 10cm, saddle speed 100cm / min by using automatic elongation measuring equipment (MEL machine, Textechno), and 200% M (modulus) load on yarn when 200% elongation of yarn. .

(2) Measurement method of dye absorption rate compared to the counter company

The dye removal rate compared with the counter yarn of the polyurethaneurea elastic yarn is computed through the following formula.

Dye absorption rate compared to the other company = dye removal rate of the polyurethane urea elastic yarn / dye removal rate of the other company

For polyurethaneurea elastic yarn and counterpart yarns, the dye removal rate of each yarn is measured using a dust rate evaluator (dye-o-meter, Dye-Cheker, Fourone system). It is a device for measuring and measuring the absorbance measured by the absorption rate.

 For the counter yarn, nylon (20-23De, amine end 33-35meq / kg) or cotton (40 male) is used. When the counterpart yarn is nylon, the dust removal rate is calculated by using the polyurethane urea elastic yarn and the nylon yarn with nylon dye (2% owf) respectively under the same acid dyeing condition. do. When the counterpart yarns are cotton yarns, the polyurethane urea elastic yarn and the cotton yarns are respectively measured using the reactive dyes of black (1% o.w.f) under the same reactive dyeing conditions to calculate the dust removal rate relative to the counterpart yarns.

[Figure] shows the dyeing conditions for each case of nylon or cotton yarn relative.

[Drawing]

Example  One

5.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 33.8 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), followed by adding 8.8 kg of 4,4'-diphenylmethane diisocyanate to 90 ° C in a nitrogen gas stream. The reaction was stirred for 120 minutes to prepare a polyurethane prepolymer having an isocyanate at the sock end. After cooling the prepolymer to room temperature, 66.1 kg of dimethylacetamide was added as a solvent to obtain a polyurethane prepolymer solution.

Subsequently, 1.1 kg of ethylenediamine as a chain extender and 0.1 kg of diethylamine as a chain terminator were dissolved in 15.6 kg of dimethylacetamide, and added to the prepolymer solution at 10 ° C. or lower, and the number of amine ends of the polyurethaneurea solution solid was 63 meq. A polyurethaneurea solution of / kg was obtained.

Further, the polyurethaneurea solution contained 1.5% by weight of triethylene glycol-bis-3- (3-tertylbutyl-4-hydroxyphenyl) propionate as an antioxidant and 1% by weight of melamine polyphosphate as an inorganic chlorinating agent. Polyurethaneurea spinning stock solution was prepared by mixing 4% by weight of hydrotalcite (Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O) coated with% and 0.5% by weight of titanium dioxide as a light-resistant agent.

The spinning stock solution obtained as described above was spun at a speed of 900 m / min by dry spinning to prepare a polyurethane urea elastic yarn having 40 denia 3 filaments and an amine terminal number of yarn of 33 meq / kg.

Example 2

In the process of preparing the prepolymer of Example 1, 10.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 32.0 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), and then 4,4'-diphenylmethane di 8.7 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 3

During the preparation of the prepolymer of Example 1, after mixing 20.0 mol% of polyethylene glycol (molecular weight 2000) to 28.2 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), 4,4'-diphenylmethanedi 8.7 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Example 4

During the preparation of the prepolymer of Example 1, 30.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 25.2 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), and then 4,4'-diphenylmethane di 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 1

Example 1 and the manufacturing process was carried out in the same manner, a polyurethane urethane elastic yarn was prepared without mixing polyethylene glycol in the prepolymer preparation step.

Comparative Example 2

During the preparation of the prepolymer of Example 1, after mixing 4.0 mol% of polyethylene glycol (molecular weight 2000) with 34.2 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), 4,4'-diphenylmethane di 8.8 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 3

During the preparation of the prepolymer of Example 1, 35.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 23.4 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), and then 4,4'-diphenylmethane di 8.9 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

Comparative Example 4

During the preparation of the prepolymer of Example 1, 40.0 mol% of polyethylene glycol (molecular weight 2000) was mixed with 21.6 kg of polytetramethylene ether glycol (PTMG, molecular weight 1800), and then 4,4'-diphenylmethane di 8.8 kg of isocyanate was added and reacted with stirring at 90 ° C. for 120 minutes in a nitrogen gas stream to prepare a polyurethane prepolymer having an isocyanate at the sock end. Since the manufacturing process is the same as in Example 1.

The properties of the polyurethaneurea elastic yarns obtained by the examples and the comparative examples are shown in Table 1 below.

division PEG content 200% M Nylon contrast
Dye reduction Cotton contrast
Dye reduction Process applicability (radiation fairness) Example 1 5 7.3 0.73 0.52 Good Example 2 10 7.0 0.89 0.60 Good Example 3 20 6.8 0.93 0.68 Good Example 4 30 6.5 0.99 0.84 Good Comparative Example 1 0 8.0 0.10 0.13 Good Comparative Example 2 4 7.2 0.48 0.44 Good Comparative Example 3 35 5.7 1.05 0.95 Inadequate Comparative Example 4 40 5.0 1.10 1.05 Inadequate

Comparative Example 1 does not contain PEG, so the dye absorption rate is very low compared to the counterpart, and the dyeability is insignificant.

In the case of Comparative Example 2, the PEG content is less than 5, the dye absorption rate is less than 0.5 relative to the other company, there is a problem in the dyeability of the spandex on the fabric and there is a problem that grin through occurs.

In case of Comparative Example 3, the modulus of the yarn is lowered due to excessive addition of PEG, and there is a problem in the process application due to insufficient workability during spinning.

In the case of Comparative Example 4 due to the excessive addition of PEG due to insufficient spinning workability there is a problem in the process application.

In the case of Examples 1 to 4, the dye absorption rate is 0.5 times or more relative to the counterpart yarn, and the spandex shows a similar level of dyeability to the counterpart yarn on the fabric, and uniform dyeing is possible.

Claims (5)

(a) a polyol comprising a first polyol and a second polyol; (b) at least one diisocyanate; (c) at least one diamine chain extender; And (d) a product obtained by reacting at least one amine chain terminator, a polyurethaneurea elastic yarn,
The second polyol is polyethylene glycol, the first polyol and the second polyol are different materials,
Polyurethane urea elastic yarn with improved dyeability, characterized in that the dye absorption rate is 0.5 times or more compared to the counterpart yarn. According to claim 1, Polyethylene glycol is a polyurethane urea elastic yarn with improved dyeability, characterized in that the mixing of 5.0 to 30.0 mol% relative to the total polyol. The polyurethane urea elastic yarn with improved dyeability according to claim 1, wherein the amine terminal number of the polyurethane urea elastic yarn is 20.0 to 45.0 meq / kg. 2. The polyurethaneurea elastic yarn according to claim 1, wherein the counterpart yarn is nylon or cotton. 2. The polyurethaneurea elastic yarn according to claim 1, wherein the dye is an acid dye or a reactive dye.