FUNCTIONAL COPPER SULFIDE COMPOSITION AND A FUNCTIONAL FIBER PRODUCED THEREFROM

Abstract

The present invention relates to a functional copper sulfide composition and a functional fiber prepared therefrom, and more particularly, a functional copper sulfide composition comprising a copper salt, a metal salt, a reducing agent, a sulfur compound, a catalyst, a polyvalent amine, an alkali compound and a pH adjusting agent; and a functional fiber prepared by treating the composition with a fiber.

The present invention can provide a functional fiber with excellent conductivity, washing resistance, washability, durability, moisture resistance and alkali resistance, wherein the color of the fiber is maintained even when it is washed repeatedly or used for a long time.

In addition, the present invention can provide a functional fiber which has excellent an antibacterial, deodorant, far-infrared radiation, wound healing, skin aging prevention, insulation, electromagnetic shielding and static electricity removal characteristics, and can be widely used in clothing, industrial and military field such as clothing, socks, gloves, bands, abdominal binder, masks, hats, bandage, scarf, bedclothes, burn pad, a hospital gown, an industrial filter and filler.

Claims

1. A functional copper sulfide composition comprising a copper salt, a metal salt, a reducing agent, a sulfur compound, a catalyst, a polyhydric amine, an alkali compound and a pH adjusting agent.

2. The composition according to claim 1, wherein the composition comprises 10 to 40% by weight of the copper salt, 1 to 10% by weight of the metal salt, 5 to 30% by weight of the reducing agent, 5 to 30% by weight of the sulfur compound, 1 to 5% by weight of the catalyst, 1 to 10% by weight of the polyhydric amine, 1 to 10% by weight of the alkali compound and 1 to 5% by weight of the pH adjusting agent,

3. The composition according to claim 1, wherein the copper salt is one or more selected from the group consisting of cupric sulfate salt, cupric chloride salt, cupric nitrate salt, cupric acetate salt and cupric sulfate ammonium salt; the metal salt is an inorganic acid salt or an organic acid salt of a metal selected from the group consisting of gold, silver, platinum, nickel, manganese, cobalt, chromium, zinc, palladium, rhodium, ruthenium, osmium, magnesium, iron and iridium; the reducing agent is one or more selected from the group consisting of metal copper, hydroxylamine, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphate, sodium hypophosphite, sodium hydrogen sulfite, glucose and phenyl compounds; the sulfur compound is one or more selected from sodium sulfide, sulfur dioxide, sulfurous acid, sodium sulfite, sodium hydrogen sulfite, sodium pyrosulfite, hyposulfurous acid, sodium hydrosulfite, sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, thiourea dioxide, hydrogen sulfide, formaldehyde sodium sulfoxylate; the catalyst is one or more selected from the group consisting of magnesium chloride, potassium chloride, calcium chloride, zinc acetate, ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium nitrate; the polyhydric amine is one or more selected from the group consisting of methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylenediamine, heptamethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine; the alkali compound is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; and the pH adjusting agent is at least one selected from sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, citric acid, acetic acid and salts thereof.

4. A functional fiber which is produced by treating one or more fibers selected from a plant fiber, an animal fiber, a synthetic fiber and a recycle fiber with the functional copper sulfide composition according to claim 1, wherein the surface of the fiber is coated with at least one functional group selected from a thiol group, thiocarbonyl group, thiourea group, azol group, an amino group, a cyano group and an amide group, a copper sulfide and a metal sulfide are coordinately bonded to the functional group, the functional group is 1 to 10% by weight based on the total fiber weight, the copper sulfide is 1 to 15% by weight based on the total fiber weight, and the metal sulfide is 0.1 to 5% by weight based on the total fiber weight.

5. The functional fiber according to claim 4, wherein the functional fiber has the far-infrared emissivity of 0.895% or more at 37 C. and 5 to 20 m, the far-infrared radiation energy of 3.4510.sup.2 W/m.sup.2.Math.m or more, the far-infrared emissivity after 40 times of washing of 0.892% or more, and the far-infrared radiation energy after 40 times of washing of 3.4110.sup.2 W/m.sup.2.Math.m or more.

6. The functional fiber according to claim 4, wherein the functional fiber has at least one function selected from the group consisting of antibacterial, deodorant, far-infrared radiation, wound healing, skin aging prevention, thermal storage and thermal insulation, electromagnetic shielding and static elimination.

7. A molded article comprising the functional fiber according to claim 4, wherein the molded article includes clothing, socks, gloves, bands, abdominal binder, masks, hats, bandage, scarf, bedclothes, burn pad, a hospital gown, or an industrial filter.

Description

DESCRIPTION OF THE INVENTION

[0083] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The following examples are illustrated only for the purpose of carrying out the invention, but the present invention is not limited thereto.

EXAMPLE 1

[0084] 35% by weight of cupric sulfate pentahydrate, 5% by weight of silver nitrate, 20% by weight of ferrous sulfate, 20% by weight of sodium thiosulfate, 3% by weight of magnesium chloride, 7% by weight of trimethylene diamine, 7% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0085] Silane coupling agent was prepared by reacting imidazole with 3-mercaptopropyltrimethoxysilane.

[0086] The polyamide fiber was impregnated in the aqueous solution containing the silane coupling agent and reacted at 50 C. for 60 minutes to prepare a surface-treated polyamide fiber.

[0087] As a result of comparing the fiber weights before and after introducing the functional group onto the surface of the fiber, the content of functional group was 2.3% by weight based on the total fiber weight.

[0088] An aqueous solution containing 60 parts by weight of the functional copper sulfide composition was prepared.

[0089] After immersing 100 parts by weight of the surface treated polyamide fibers in the aqueous solution, the reaction was carried out at 60 for 2 hours. The bath ratio of the polyamide fiber and the aqueous solution was 1:20.

[0090] The reaction-finished fibers were washed several times with room temperature and with hot water at 50 C. to remove unreacted materials, and then dried with hot air at 80 C. to obtain a functional polyamide Fiber.

[0091] As a result of comparing the fiber weights before and after reacting the functional copper sulfide composition with the functional group-introduced fiber, and performing SEM-EDS analysis of functional fiber, the content of copper sulfide was 11.5% by weight based on the total fiber weight and the content of silver sulfide was 1.8% by weight.

EXAMPLE 2

[0092] 35% by weight of cupric sulfate pentahydrat , 5% by weight of silver nitrate, 20% by weight of ferrous sulfate, 22.5% by weight of sodium thiosulfate, 0.5% by weight of magnesium chloride, 7% by weight of trimethylene diamine, 7% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0093] The same procedures as in Example 1 were carried out except that above functional copper sulfide composition was used.

[0094] The content of copper sulfide was 9.8% by weight based on the total fiber weight, and the content of silver sulfide was 1.5% by weight.

EXAMPLE 3

[0095] 35% by weight of cupric sulfate pentahydrate, 5% by weight of silver nitrate, 20% by weight of ferrous sulfate, 17% by weight of sodium thiosulfate, 10% by weight of magnesium chloride, 5% by weight of trimethylene diamine, 5% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0096] The same procedures as in Example 1 were carried out except that above functional copper sulfide composition was used.

[0097] The content of copper sulfide was 9.1% by weight based on the total fiber weight, and the content of silver sulfide was 1.3% by weight.

COMPARATIVE EXAMPLE 1

[0098] The same procedures as in Example 1 were carried out except that silver nitrate was not used.

[0099] 35% by weight of cupric sulfate pentahydrate, 22.5% by weight of ferrous sulfate, 22.5% by weight of sodium thiosulfate, 3% by weight of magnesium chloride, 7% by weight of trimethylene diamine, 7% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0100] The content of copper sulfide was 7.9% by weight based on the total fiber weight

COMPARATIVE EXAMPLE 2

[0101] The same procedures as in Example 1 were carried out except that magnesium chloride was not used.

[0102] 35% by weight of cupric sulfate pentahydrate, 5% by weight of silver nitrate, 22% by weight of ferrous sulfate, 21% by weight of sodium thiosulfate, 7% by weight of trimethylene diamine, 7% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0103] The content of copper sulfide was 6.5% by weight based on the total liber weight, and the content of silver sulfide was 0.8% by weight.

COMPARATIVE EXAMPLE 3

[0104] The same procedures as in Example 1 were carried out except that trimethylene diamine was not used.

[0105] 35% by weight of cupric sulfate pentahydrate, 5% by weight of silver nitrate, 23.5% by weight of ferrous sulfate, 23.5% by weight of sodium thiosulfate, 3% by weight of magnesium chloride, 7% by weight of sodium hydroxide and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0106] The content of copper sulfide was 5.5% by weight based on the total fiber weight, and the content of silver sulfide was 0.6% by weight.

COMPARATIVE EXAMPLE 4

[0107] The same procedures as in Example 1 were carried out except that sodium hydroxide was not used.

[0108] 35% by weight of cupric sulfate pentahydrate, 5% by weight of silver nitrate, 23.5% by weight of ferrous sulfate, 23.5% by weight of sodium thiosulfate, 3% by weight of magnesium chloride, 7% by weight of trimethylene diamine and 3% by weight of citric acid were mixed to prepare a functional copper sulfide composition.

[0109] The content of copper sulfide was 7.5% by weight based on the total fiber weight, and the content of silver sulfide was 1.1% by weight.

[0110] The specific resistance, far infrared rays emissivity, washing resistance, durability, copper sulfide content, silver sulfide content and functional group content of the polyamide fiber prepared from the above Examples and Comparative Examples were measured, and the results are shown in Table 1 and 2 below.

(Specific Resistance; Resistivity)

[0111] The specific resistance (.Math.cm) of fibers prepared according to KS K 0180 (Test Method for Electrical Resistance of Yarns, 2013), was measured.

(Far-infrared Rays Emissivity)

[0112] According to the measurement method (KFIA-FI-1005) of far infrared ray emissivity and radiation energy by infrared spectrophotometer, the light source (infrared lamp, 150 W) was irradiated to the specimen at the temperature of 37 C., the distance between the specimen and light source of 62 cm for 20 minutes, and then the far-infrared emissivity (%) and the far-infrared radiation energy (W/m.sup.2.Math.m) at a wavelength of 5 to 20 m were measured using FT-IR spectrometer.

(Washing Resistance)

[0113] The washing resistance test of fibers is carried out by the washing fastness test method prescribed in KS K 0430.

[0114] Specifically, 2 g of the fiber was dissolved into a stainless steel container containing 100 m of a solution containing 5 g/L of a commercial detergent, and then 10 steel beads was put in container.

[0115] The container was washed in a washing fastness tester maintained at 40 C. for 30 minutes. After washing, the sample was rinsed with water and then dried to below 60 C. This washing process is repeated a predetermined number of times, and then the discoloration and the specific resistance were measured.

(Durability)

[0116] 1 g of the fiber was quantitatively measured, and then was put in a thereto-hygrostat maintained at a temperature of 60 C., and a relative humidity of 95%.

[0117] The discoloration and specific resistance of the fibers were measured every 12 hour.

(Content of Copper Sulfide, Content of Silver Sulfide and Content of Imidazole Group)

[0118] The weight of the fibers before and after the introduction of the functional group onto the surface of the fiber was compared, and the content of functional groups was determined.

[0119] The functional copper sulfide composition is reacted with the fiber into which the functional group is introduced, and the weight before and after reaction was compared, and the elemental content was determined by SEM-EDS analysis of the functional fiber.

[0120] The content of copper sulfide and silver sulfide was determined by above measurement.

TABLE-US-00001 TABLE 1 Durability After 50 washings (color specific specific change resistance resistance Color after color ( .Math. cm) ( .Math. cm) change 48 hrs) Example 1 Olive green 2.6 10.sup.1 4.4 10.sup.1 No No change change Example 2 Olive green 7.8 10.sup.1 6.1 10.sup.0 No No change change Example 3 Olive green 8.2 10.sup.1 7.0 10.sup.0 No No change change Comparative Olive blue 2.5 10.sup.1 5.8 10.sup.4 Change Change Example 1 Comparative Olive brown 1.3 10.sup.2 6.2 10.sup.3 Change Change Example 2 Comparative Olive brown 3.5 10.sup.2 8.5 10.sup.3 Change Change Example 3 Comparative Olive blue 9.6 10.sup.1 2.2 10.sup.3 Change Change Example 4

[0121] From the results shown in Table 1, the functional fibers of Examples 1 to 3 show low resistivity and excellent washing resistance because copper sulfide and silver sulfide are formed on the surface of the fibers. And the durability is excellent in even under the conditions of high temperature and high humidity.

[0122] In particular, in Example 1 in which the content of magnesium chloride used as a catalyst was adjusted to 3 wt %, the resistivity, the washing resistance and the durability were superior to those in Example 2 the content of magnesium chloride: 0.5% by weight) and Example 3 (magnesium chloride content: 10% by weight).

[0123] On the other hand, in Comparative Examples 1 to 4, resistivity, washability and durability were lower than those of Examples 1 to 3.

[0124] In particular, in the case of Comparative Example 1 in which silver nitrate used as a metal salt was not used, it can be seen that the washing resistance and the durability are the most inferior.

TABLE-US-00002 TABLE 2 After 40 washings Far-infrared rays Far-infrared radiation rays Far-infrared Emissivity energy Emissivity radiation energy (%) (W/m.sup.2 .Math. m) (%) (W/m.sup.2 .Math. m) Example 1 0.901 3.49 10.sup.2 0.899 3.46 10.sup.2 Example 2 0.895 3.45 10.sup.2 0.892 3.41 10.sup.2 Example 3 0.896 3.47 10.sup.2 0.894 3.41 10.sup.2 Comparative 0.891 3.42 10.sup.2 0.879 3.38 10.sup.2 Example 1 Comparative 0.888 3.40 10.sup.2 0.881 3.39 10.sup.2 Example 2 Comparative 0.889 3.41 10.sup.2 0.882 3.38 10.sup.2 Example 3 Comparative 0.891 3.41 10.sup.2 0.880 3.37 10.sup.2 Example 4

[0125] From the results of the above Table 2, the functional fibers of Examples 1 to 3 show excellent emissivity of far-infrared rays because copper sulfide and silver sulfide are formed on the surface of the fibers. And it can be seen that the emissivity remains constant even after repeated washing.

[0126] In particular, in Example 1 in which the content of magnesium chloride used as a catalyst was adjusted to 3 wt %, the far infrared ray emissivity was superior to those in Example 2 (content of magnesium chloride: 0.5% by weight) and Example 3 (content of magnesium chloride: 10% by weight).

[0127] On the other hand, in Comparative Examples 1 to 4, the far-infrared ray emissivity was much inferior to those in Examples 1 to 3.

INDUSTRIAL AVAILABILITY

[0128] The present invention can provide a functional fiber with excellent conductivity, washing resistance, washability, durability, moisture resistance and alkali resistance, wherein the color of the fiber is maintained even when it is washed repeatedly or used for a long time.

[0129] In addition, the present invention can provide a functional fiber which has excellent an antibacterial, deodorant, far-infrared radiation, wound healing, skin aging prevention, insulation, electromagnetic shielding and static electricity removal characteristics, and can be widely used in clothing, industrial and military field such as clothing, socks, gloves, bands, abdominal binder, masks, hats, bandage, scarf, bedclothes, burn pad, a hospital gown, an industrial filter and filler.