KR100674280B1 - Black dyed-polyurethane fiber and manufacturing method thereof - Google Patents

Abstract

A black dyed-polyurethane fiber and a manufacturing method thereof are provided to represent a uniform and deep black color by increasing the dispersion of the carbon black. One or more kinds of the dispersion resin selected in polyurethane, polyurethane urea and cyclohexanon aldehyde resin and the carbon black are dispersed into the organic solvent so that the carbon black slurry is manufactured. The carbon black slurry is added into the polyurethane resin and the production mixing materials is spun. At the slurry, the concentration of the carbon black and the dispersion resin is 10-30 wt %, respectively. An amount of 0.1 to 10 wt % of slurry in contrast of solid is added into the polyurethane resin.

Description

Black polyurethane yarn and its manufacturing method {BLACK DYED-POLYURETHANE FIBER AND MANUFACTURING METHOD THEREOF}

The present invention relates to a black polyurethane primary yarn and a method for producing the same, and more particularly, by dispersing carbon black into a slurry with a small amount of the resin for dispersing, to improve the dispersibility.

As a general black pigment, iron oxide (Fe ₃ O ₄ ) or carbon black may be used. However, iron oxide (Fe ₃ O ₄ ) has a specific gravity, and when heated to a temperature of about 160 ℃ in the air has a problem such as change to Fe ₂ O ₃ discoloration and easy to magnetize (磁). Carbon black, on the other hand, has been widely used because of its low manufacturing cost and good fiber properties when applied to fibers.

However, carbon black is hydrophobic, as described in Korean Patent Publication No. 2002-0092588, and has a disadvantage in that it may not develop a dark color depending on the type of material and polymer applied. It may need to be added. In this case, it is difficult to uniformly disperse the carbon black, agglomeration between the carbon black occurs, and the replacement cycle of the spinning nozzle and the filter is shortened, and there is a problem that the color of the fabric is not uniform.

It is therefore an object of the present invention to provide a polyurethane primary yarn having a uniform color and a deep black color produced by improving the dispersibility of carbon black and a method for producing the same.

In order to achieve the above object, in the present invention, the carbon black slurry is prepared by dispersing at least one resin and carbon black selected from polyurethane, polyurethane urea, and cyclohexanone aldehyde resin in an organic solvent. Provided is a method for producing a black polyurethane primary yarn comprising adding to a polyurethane resin to spun the resulting kneaded product.

In another aspect of the present invention there is also provided a black polyurethane primary yarn obtained by the above method and a fabric made by knitting it with a polyamide yarn or a polyester yarn.

Hereinafter, the present invention will be described in more detail.

Polyurethane resin used in the production of black polyurethane primary yarn of the present invention is prepared by reacting organic diisocyanate and polymer diol in a conventional manner to prepare a polyurethane precursor, and then dissolved it in an organic solvent and then used as a chain extender. It is prepared by reacting diamine with a monoamine used as chain terminator.

As organic diisocyanate, 4.4'- diphenylmethane diisocyanate, 1,5'- naphthalene diisocyanate, 1,4'- phenylene diisocyanate, hexamethylene diisocyanate, 1,4'- cyclohexane diisocyanate, 4, Organic diisocyanates such as 4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate or mixtures of two or more thereof are available but not limited thereto.

The polymer diol may be polytetramethylene ether glycol, polypropylene glycol, polycarbonate diol, or the like.

As the diamines, one kind or a mixture of two or more kinds thereof, such as ethylenediamine, 1,2'-propylenediamine, hexamethylenediamine, xylenediamine, 4,4'-diphenylmethanediamine and hydrazine, can be used. It doesn't work.

According to the present invention, the carbon black used as the black pigment in the black polyurethane primary yarn is pre-mixed with a small amount of the resin for dispersing in consideration of its dispersibility, miscibility with the polyurethane and physical properties of the final product, and slurried. It is characterized by using after.

Specifically, in order to increase the dispersibility of the carbon black, carbon black is dispersed in an organic solvent together with the resin component for dispersing to form a slurry, and the slurry is added to the polyurethane resin and then spun to form a black polyurethane primary yarn It will be prepared.

Polyurethane, polyurethane urea, cyclohexanone aldehyde resin, etc. can be used as said dispersion resin.

Wetting agents such as conventional copolymers or block copolymer resins having a pigment affinity group, for example, acrylate copolymers, for preparing the carbon black slurry (e.g., Disperbyk-115, Disperbyk-160, BYK-9075, manufactured by BYK) , BYK-9077, etc.) and / or conventional dispersants such as high molecular weight alkylammonium and the like (for example, BYK trade name Disperbyk 140, BYK-9076, BYK-9540, etc.) are preferably added. In the carbon black slurry, the resin, the humectant, the dispersant, and the like serve to control the aggregation phenomenon by maintaining the distance between the carbon black particles and to ensure good dispersibility by penetrating between the carbon black. In addition to ensuring such dispersibility, it also ensures the viscosity of the final slurry itself, and by adding a small amount of resin to improve the miscibility of carbon black and polyurethane resin to prevent phase separation and ensure good compatibility. do.

The molecular weight of the dispersion resin used in the carbon black slurry is suitable in the range of 10000 to 100000, the viscosity is suitable for about 10 to 100 poise (poise) level. In addition, the amine value (mgKOH / g) of the humectant and dispersant is 10-50 level, the acid value (mgKOH / g) is suitable 0 0 level, but is not limited thereto.

It is preferable to add the carbon black and the resin for dispersing in the slurry within 60% by weight relative to the total weight of the slurry, but when added in excess of 60% by weight, entanglement and aggregation with the polyurethane polymer may occur.

More specifically, during the slurry preparation, carbon black and resin are dispersed in an organic solvent so as to be in a range of 10-30% by weight relative to the total weight of the slurry. More preferably, the carbon black and resin are each 10-20% by weight based on the total weight of the slurry. Add as much as possible. When the amount of carbon black and resin to be added exceeds 30% by weight, the viscosity of the entire slurry may be increased by agglomeration of carbon black or the high viscosity of the resin itself, thereby lowering the fluidity of the polymer. If less than, the dispersibility of the carbon black may be lowered.

In addition, the wetting agent and the dispersing agent are suitable for the dispersion of carbon black, respectively, within the range of 10% by weight is appropriate, and when it exceeds 10% by weight, there is a fear of forming a gel with a polyurethane polymer (gel).

In the present invention, the amount of carbon black used varies depending on the type, particle size, specific gravity, and the like, but is preferably 0.1 to 10% by weight based on the final polymer solid content of the raw material. If the amount is less than 0.1% by weight, the resulting fibers are inferior in color and cause color unevenness. If the amount is more than 10% by weight, loss of performance as an elastic fiber and poor spinning workability occur.

In the present invention, the particle size of the carbon black is preferably 0.1 to 1000 nm. If the particle size is less than 0.1 nm, the dispersed state in the solvent or polymer may be good, but it may be recovered with N, N'-dimethylacetamide by high pressure air during solvent recovery, and the particle size is 1000 nm. If exceeded, agglomeration of particles may occur, resulting in problems such as uneven color (especially red or blue) and workability deterioration.

Carbon black having the above characteristics may be used by grinding and dispersing in an attrition mill, a sand grinder or a high speed mixer in order to make the primary particle size uniform.

Other fillers may include UV stabilizers, antioxidants, NOx gas anti-yellowing agents, anti-sticking agents, dyeing enhancers, chlorine resistant agents, matting agents, and the like.

In the present invention, the spinning method is not particularly limited, and dry spinning, wet spinning, melt spinning, and the like except for chemical spinning can be used, and it is particularly effective to use dry spinning.

In addition, examples of the organic solvent include N, N'-dimethylformamide, N, N'-dimethylacetamide, tetramethylurea and hexamethylphosphonoamide.

Hereinafter, the present invention will be described in more detail based on the following Examples and Comparative Examples. However, the following Examples and Comparative Examples are not intended to limit the invention only.

In the following examples, the carbon black was washed with distilled water, and the carbon black having an average particle size of about 20 nm was repeated three to four times in a centrifuge, and then completely dried in a drying oven. Used after removing impurities.

Example 1

518 g of diphenylmethane-4,4'-diisocyanate and 2328 g of polytetramethylene ether glycol (molecular weight 1800) were reacted with stirring at a temperature of 85 ° C. for 90 minutes under a nitrogen gas stream, and a polyurethane precursor containing an isocyanate at both terminals was stirred. After the preparation, the mixture was cooled to room temperature, and 4643 g of dimethylacetamide was added thereto and dissolved to prepare a polyurethane precursor.

Subsequently, a solution of 54 g of propylenediamine and 9.1 g of diethylamine in 1889 g of dimethylacetamide was added to the polyurethane precursor solution at 10 ° C. or lower to prepare a segmented polyurethane polymer solution. The polyurethane resin was prepared by adding other additives such as a conventional UV stabilizer, an antioxidant, a yellowing inhibitor, a dye enhancer, a magnesium-based anti-sticking agent, a titanium-based matting agent, and the like to the polymer.

20% by weight of the carbon black and the polyurethane resin, respectively, are high molecular weight block copolymer resins having a pigment affinity group, BYK's Disperbyk-160 and BYK's BYK-9076 high molecular weight alkyl ammonium. Carbon black slurry was prepared by using 3% by weight of silver and dimethylacetamide as a solvent to be 54% by weight.

The prepared slurry was added to the polyurethane resin so as to be 0.5% by weight relative to the weight of the final polymer solids based on the carbon black content, followed by stirring to obtain a fiber raw material having a viscosity of 4000 poise. This raw material was spun using a conventional dry spinning method to prepare a polyurethane denier yarn of 20 denier.

Polyurethane yarns and polyamide-based yarns were knitted with a teaching material and then dyed using Black MR (Ciba), an acid dye. After wash | cleaning and dissolving this and isolate | separating a polyurethane primary yarn, the wash fastness of this was measured.

Example 2

Polyurethane native yarn prepared in the same manner as in Example 1 was knitted with polyester yarn and a teaching fabric, and then dyed with Black XLDF (M. Dohmen), a disperse dye. After wash | cleaning and dissolving this and isolate | separating a polyurethane primary yarn, the wash fastness of this was measured.

Example 3

The carbon black slurry was prepared in the same manner as in Example 1 except that the cyclohexanone aldehyde resin was used instead of the polyurethane.

Subsequently, the slurry was subjected to the same method as in Example 1 except that the carbon black was added to the polyurethane so that 3.0 wt% of the final polymer solids was obtained, and thus, a polyurethane original yarn was obtained and its washing fastness was measured.

Example 4

The original yarn prepared in the same manner as in Example 3 was knitted with polyester yarn and a teaching fabric, and then dyed with Black XLDF (M. Dohmen), a disperse dye. This was washed and decomposed to separate the polyurethane raw yarn, and then the washing fastness thereof was measured.

Example 5

The carbon black slurry was prepared in the same manner as in Example 1 except that 10 wt% of polyurethane and polyurethane urea resin were used instead of 20 wt% of polyurethane, respectively. Subsequently, the slurry was subjected to the same method as in Example 1 except that the carbon black was added to the polyurethane so that 7.0 wt% of the final polymer solids was obtained, thereby obtaining a polyurethane primary yarn, and the washing fastness thereof was measured.

Example 6

The original yarn prepared in the same manner as in Example 5 was knitted with polyester yarn and a teaching fabric, and then dyed with Black XLDF (M. Dohmen), a disperse dye. This was washed and decomposed to separate the polyurethane raw yarn, and then the washing fastness thereof was measured.

Comparative example  One

Except that carbon black was not added at the time of polyurethane fiber production was carried out in the same manner as in Example 1 to prepare a polyurethane elastic yarn and to measure its laundry fastness.

Comparative Example 2

Carbon black-added polyurethane elastic yarn prepared in the same manner as in Comparative Example 1 was knitted with a polyester yarn and a cross-woven fabric, and then dyed with Black XLDF (M. Dohmen) as a disperse dye. This was washed and decomposed to separate the polyurethane elastic yarn, and then the washing fastness thereof was measured.

Comparative Example 3

The carbon black slurry was prepared by dispersing only carbon black in dimethylacetamide (DMAc) without a resin component at high speed to obtain a slurry, and adding the same to the polyurethane polymer in the same manner as in Example 1 except that the slurry was added to the polyurethane polymer in an amount of 0.5%. Was prepared and its washing fastness was measured.

Comparative Example 4

The original yarn prepared in the same manner as in Comparative Example 3 was knitted with polyester yarn and a teaching fabric, and then dyed with Black XLDF (M. Dohmen), which is a disperse dye. After wash | cleaning and dissolving this and isolate | separating a polyurethane primary yarn, the wash fastness of this was measured.

The physical property evaluation method of the product manufactured in the said Example and the comparative example is as follows, The evaluation result is shown in Table 1.

o Elongation: Measure by using Universal Testing Machine (UTM) at 5cm of sample length and 50cm / min of tensile speed.

o Chromaticity evaluation: The spectral reflectance of the primary sand in each condition was measured using a spectrophotometer (color-eye 7000, Macbeth). The K / S value obtained from the Kubelka Munk equation is expressed as the sum (area) of the K / S values for each wavelength (360 to 750 nm). When the reflectance is large (low concentration), it shows a low K / S value, and when the reflectance is small (absorption, dark concentration), it shows a large K / S value. In general, when comparing the contrast, such as the concentration-by-contrast, it is represented by the sum of K / S, and the L * value, a * value, and b * value are also measured through color coordinates to know the color.

o Color fastness: measured by KS K 0430 AI method.

o Carbon Black Slurry Filterability: A pressure of ² kg / cm ² was applied to a 20 weight% carbon black slurry to determine whether the filtration was performed in a 15 μm sieve. In other words, if the slurry of 1000ml is injected and pressurized 900ml of the slurry comes out, it shows 90% filterability, and the higher the value, the better the filterability.

o Filter replacement cycle: The polyurethane raw material mixed with the carbon black slurry was passed through a 40 μm bag filter installed just before spinning. Then, the pressure change over time was measured and the replacement cycle was measured. However, the pressure gauge was installed after the filter.

The better the dispersibility of the polyurethane raw material, the longer the replacement cycle, and the filter replacement was carried out when the pressure was less than 12kg / cm ² . The initial filter pressure was about 30 kg / cm ² .

As shown in Table 1, it can be seen that in Comparative Examples 1 and 2 without adding carbon black, the K / S area is much lower than that of Examples 1 to 6, and thus the color density is lowered. In the case of Comparative Example 3 and Comparative Example 4, in which the resin was not used in the preparation of the slurry, carbon black was not dispersed, and thus the filterability was remarkably decreased, and the replacement cycle of the filter was only one day. .

By using the carbon black slurry containing the resin component according to the present invention, it is possible to produce a polyurethane primary yarn with high color and high depth by uniform dispersion of carbon black with excellent productivity. In addition, the polyurethane yarn thus prepared is not only capable of thick dyeing when dyed in black after being inclined with nylon yarn or polyester yarn, it can also provide excellent washing fastness.

Claims (6)

Dispersion of at least one dispersion resin and carbon black selected from polyurethane, polyurethane urea and cyclohexanone aldehyde resin in an organic solvent to prepare a carbon black slurry, and then adding the carbon black slurry to the polyurethane resin Method for producing a black polyurethane primary yarn comprising spinning the water. The method according to claim 1, wherein the concentration of the carbon black and the resin for dispersion in the slurry is 10-30% by weight, respectively. The method of claim 1, wherein the slurry is added to the polyurethane resin in an amount of 0.1 to 10% by weight based on carbon black relative to the final polymer solid content of primary use. The method according to claim 1, wherein the dispersing agent, the wetting agent, or a mixture thereof is further added when preparing the carbon black slurry. The black polyurethane primary yarn manufactured by the manufacturing method of any one of Claims 1-4. A woven or knitted fabric comprising the black polyurethane primary yarn of claim 5.