TW201437444A - Manufacturing method of bamboo cellulose fiber with natural antimicrobial, deordorization, and negative ion functions - Google Patents

Abstract

This invention provides a manufacturing method of a bamboo cellulose fiber with natural antimicrobial, deordorization, and negative ion functions. The manufacturing method is to add an appropriate amount of coffee residue into the bamboo pulp to form a base material. The N-methylmorpholine N-oxide (also known as NMMO) solvent is then added and mixed into the base material to form the dope. The dope is squeezed out of a spinneret by Dry-jet Wet Spinning, and solidified when placed in a solidifying bath to form the filament. Finally, apply the rinsing, drying, oiling, and rolling up processes respectively to obtain the bamboo cellulose fiber with natural antimicrobial, deordorization, and negative ion functions.

Description

Method for preparing bamboo cellulose fiber with natural antibacterial, deodorizing and negative ion functions

The invention relates to a "preparation method of bamboo cellulose fiber with natural antibacterial, deodorizing and negative ion function", which belongs to the technical field of bamboo fiber manufacturing, and adopts an environmentally friendly process which does not cause environmental pollution, and the obtained bamboo cellulose The fiber is a filament, or can be cut into staples according to the required length. Both have good antibacterial, deodorizing and negative ions functions, and can be applied to textiles, medical materials and biological materials. Technology and other uses.

At present, the largest amount of raw materials used in the production of synthetic fibers, in the order of polypropylene (PP), polyester (PET), polyethylene (PE) and nylon (Nylon), accounted for 96% of the total use, when these When a large amount of synthetic synthetic fiber is made into a fabric and becomes waste after being used, it cannot be decomposed by the natural environment and poses a great hazard to the environment. Therefore, pulp is used as a raw material and a solvent method is used for production. Natural cellulose fibers have become mainstream, and the waste of their fabric products is called green fiber or Lyocell fiber because it can be naturally degraded.

According to the research and development of the technology and development of the bamboo charcoal in the textile industry published by the Forestry Commission of the National Agricultural Commission, and the new regenerated cellulose fibrin-bamboo fiber raft published in the second issue of China Textile Science and Technology Journal in 2003, Bamboo fiber has natural antibacterial, moisture absorption and ventilation, negative ion health care and other characteristics, and bamboo is a fast-growing plant with strong fertility (2 to 3 years can be felled), easy to update, is an excellent renewable resource, in the process of resource utilization. There will be no problems such as serious damage to the environment and ecology of the forest land when the trees are felled. In addition, the cost of bamboo pulp is only one-third of that of wood pulp. Therefore, the solvent method of manufacturing Lyocell fiber is used as bamboo fiber. It has been found in many patent documents, such as: Chinese invention patents CN1129680, CN1190531, CN1315624, and CN100395384, etc. It is known from the disclosure of the various Chinese invention patents disclosed that the bamboo fiber produced by the invention does not have the deodorizing effect.

According to the statistics of the Customs Bureau of the Ministry of Finance of Taiwan, the import of coffee beans in 2011 The amount of waste coffee grounds after baking is at least 8,842 metric tons (the ratio of coffee beans to after use is about 2:1). At present, most of the waste coffee grounds of more than 8842 metric tons per year are It is treated by direct incineration or burial, and a small part is used to remove odor due to the deodorizing effect of coffee slag, or as a nutrient for supplying plants, or as a function of cleaning; in addition, it has been applied For the production of coffee yarn, for example, the Republic of China invention patent No. I338729, the technical content disclosed by the coffee yarn can be known that the coffee slag and the high molecular polymer particles are mixed into a masterbatch, and then the masterbatch is drawn. The yarn is formed, and the polymer polymer particles used are selected from the group consisting of polypropylene, nylon, and polyester. Therefore, the fabric obtained by the coffee yarn contains a polymer, so when it is used as waste, Will not be decomposed by the natural environment, there will still be a result of harm to the environment.

In addition to the abundant bamboo forest resources in Taiwan (the area of bamboo forest is 150,000 hectares, accounting for 7.2% of the forest area), and more than 8842 metric tons of waste coffee slag per year can be used for deodorization. The present inventors have in particular In-depth study on how to combine the bamboo fiber that can be decomposed by the natural environment with the waste coffee slag with deodorizing function, and the natural antibacterial and negative ion health properties of the bamboo fiber itself, and become natural antibacterial, deodorant and The negative ion function bamboo cellulose fiber can finally complete the preparation method of the invention after repeated experiments.

The main object of the present invention is to provide a method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions, wherein an appropriate amount of coffee residue is first added to bamboo pulp as a raw material, and then added. N-methylmorpholine N-oxide (NMMO) solvent is mixed and dissolved, and heated at 80 ° C ~ 100 ° C using a vacuum film evaporator (TFE), evaporating and dissolving in 5 minutes. The mixed water is removed to 5~13% to form a dope, and the mucus is squeezed out from the spinning nozzle by Dry-jet Wet Spinning and passed through the coagulation bath. After solidification and re-generation of silk, and finally by washing, drying, oiling and coiling, etc., a filament can be obtained, or the natural antibacterial can be cut into staples according to the required length. , deodorizing and negative ion function bamboo cellulose fiber; its overall process is short and uses non-toxic oxidized methyl marlin as a solvent, and through the solvent recovery methods such as decolorization, filtration, concentration and refining, it can oxidize methyl marin Solvent recovery and recycling And become an environmentally friendly process that does not pollute the environment, and the bamboo produced In addition to its natural antibacterial and negative ion health benefits, cellulose fiber has deodorizing effect due to its waste coffee slag. When the finished fabric is used as waste, it can be naturally decomposed in the environment without It will cause damage to the environment.

Figure 1 is a block diagram of the manufacturing process of the present invention.

Fig. 2 is a chemical structural diagram of N-methylmorpholine N-oxide (NMMO) used in the present invention.

In order to further explain the production process and efficacy of the present invention, the following is a detailed description of the drawings and the respective test examples. As shown in FIGS. 1 and 2, the present invention has a bamboo having natural antibacterial, deodorizing and negative ion functions. The method for preparing cellulose fiber comprises the steps of: a. adding coffee residue to bamboo pulp as raw material; the waste coffee slag is firstly ground to a fine particle of 500 nm to 1000 nm (nano). Then added to the bamboo pulp, the bamboo pulp is selected from bamboo pulp cellulose with α-cellulose content of more than 80%, and the cellulose degree of polymerization (DP) is between 400 and 800; b. N-methylmorpholine N-oxide (NMMO, chemical structure shown in Figure 2) and 1,3-phenylene-bis 2-oxazoline (BOX) in step a In the bamboo pulp, it is mixed and dissolved into a dope; the waste coffee grounds are placed together with the bamboo pulp cellulose, the oxidized methyl marlin solvent and the phenyloxazole additive by using a horizontal pulping machine. After entering, the high-speed agitation is carried out at a low temperature of 60 ° C to 80 ° C, and by oxidizing methyl marlin to the fiber Vitamins have high swelling properties, high solubility and fast dissolution rate, so as to achieve rapid mixing and dissolution to form a slurry, and then use a vacuum film evaporator (TFE) to heat at 80 ° C ~ 120 ° C, The water after evaporation and dissolution in 5 minutes is removed to 5~13% to form a dope; c. Spinning by Dry-Jet Wet Spinning, the spinning mucilage After being extruded from the spinning nozzle, it enters the coagulation bath to solidify and regenerate the yarn; and d. the process of washing, drying, oiling and coiling the solidified regenerated spinning After that, a filament can be obtained, or a bamboo cellulose fiber having natural antibacterial, deodorizing and anionic properties which is cut into staples can be cut according to the required length, wherein the drying temperature is 100. °C~150°C, the coiling speed is 200~800 meters per minute, and the fiber strength of the bamboo cellulose fiber is 1.5g/d~4.0g/d, and the fiber elongation is 4.0%~8.0%. The coefficient is 50g/d~150g/d.

Wherein, the content of waste coffee grounds in the bamboo pulp added in the step a is 0.5 wt% to 5 wt%.

Among them, the 1,3-phenylene-bis 2-oxazoline (BOX) added in step b can reduce the color and the degree of polymerization of the cellulose mucilage, and the concentration of the oxidized methylmarine solvent is 50%~75% and non-toxic solvent, after being washed out in the washing process, and then recycled, the loss rate is low and the recovery rate can reach 99.7% or more. In addition to reducing the manufacturing cost, it will not cause The pollution of the environment is in full compliance with the specifications of the environmental protection process.

In another step d, the solvent recovery step after solidification regeneration and water washing comprises:

1. Decolorization: the decolorization is carried out by means of activated carbon suspension. The non-decoloring liquid is added with 0.05% to 0.10% of activated carbon powder with good adsorption and suspension, and alternately treated by blast mixing and adsorption and static suspension adsorption. The processing time ratio of the two is 1:3 to 1:6, and the processing time is more than 8 hours to complete the decolorization. This method and program can simplify the equipment, save energy and improve the adsorption decolorization effect.

2. Filtration: It adopts two-stage filtration. The first stage of coarse filtration uses a general filter-type filter to simplify the equipment. However, in order to avoid the accumulation of activated carbon in the outermost layer of the filter element and slow down the filtration speed, the filter aid is pre-clothed. In addition to the surface of the filter element, 0.03%~0.05% is also added to the unfiltered filtrate, so that the filtrate does not have a small amount of bulking filter aid, the filtration speed is greatly improved and can be maintained without any decrease. The filter aid is composed of diatomaceous earth. The ratio of cellulose=4:1 is the best. After the coarse filtration is completed, the residual residue of the residue is centrifuged, dehydrated and recovered, and the filter residue of the filter residue after dehydration still has the filter effect and can be reused once. The second stage of fine filtration uses the precision filter UF. After the fine filtration, the filtrate has the same cleanness as the fresh solvent. The coarse filtration and fine filtration of this method can achieve low equipment cost, low loss rate, high throughput and high purity. Features.

3. Concentration: When the process of the invention is recovered by the water washing liquid, the solvent concentration thereof is required to be concentrated from 6.5% to 8.0% to 50% to 55%, and about 90 tons of water per ton of fiber is required to be concentrated and concentrated. Large; when the fiber production is small: it adopts three-effect concentration method, and its water removal requires about 0.5 tons of steam per ton (although the steam consumption is high, but the power consumption is small); when the fiber production is slightly larger: the MVR is adopted. In the concentration mode, the water removal requires about 0.003~0.03 tons of steam per ton (although the steam consumption is low, but the power consumption is slightly larger), the two kinds of concentration methods are different for different yields, but the concentrated liquid and condensed water produced can be all Recycling; wherein the concentrate is used for the process solvent; the condensed water can be used for washing the raw silk.

4. Refining: low temperature oxidation and neutralization reduction at 80 °C, using 35% H2O2 as oxidant, 85% N2H4. H2O is a neutralizing reducing agent, and the result of redox determination by potentiometric titration can reduce the NMM content to below 10 ppm, which can improve the purity of NMMO and reduce the loss.

In order to further prove the efficacy of the present invention, according to the process of the present invention, different components, conditions and parameters are set, and the following examples of the tests are completed, and the following are explained in detail:

Example 1: (Sample Nos. 1 to 6 were prepared according to the method of the present invention):

The waste coffee grounds is added to a slurry of bamboo pulp cellulose having a polymerization degree of 500 and a solvent of oxidized methyl marlin (NMMO), and mixed with 1,3-phenylene-bis 2-oxazoline in different proportions. , BOX) stabilizer, then use vacuum film evaporator to evaporate excess water, heat at 80 ° C ~ 120 ° C, remove water to 5% ~ 13% within 5 minutes, you can dissolve bamboo pulp cellulose into mucus (dope Then, the mucus is sent to a spinning machine for spinning by a metering pump, and is extruded by a spinning nozzle by a dry-jet wet spinning method (Dry-jet Wet Spinning), and then regenerated by a coagulation bath. The bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions is prepared by washing, drying, oiling and coiling. The mucus composition of the bamboo cellulose fiber samples obtained above is shown in the sample numbers 1 to 6 in [Table 1].

Example 2: (Sample No. 7~12 prepared according to the method of the present invention):

Adding waste coffee grounds to a slurry of bamboo pulp cellulose with a degree of polymerization of 750 and oxidized methyl marlin (NMMO) solvent, and incorporating 1,3-phenylene-bis 2-oxazoline in different proportions , BOX) stabilizer, then use vacuum film evaporator to evaporate excess water, heat at 80 ° C ~ 120 ° C, remove water to 5% ~ 13% within 5 minutes, you can dissolve bamboo pulp cellulose into mucus (dope Then, the mucus is sent to a spinning machine for spinning by a metering pump, and is extruded by a spinning nozzle by a dry-jet wet spinning method (Dry-jet Wet Spinning), and then regenerated by a coagulation bath. The bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions is prepared by washing, drying, oiling and coiling. Mucus of bamboo cellulose fiber sample obtained above The composition table is shown in sample No. 7~12 in [Table 1].

Example 3: Performing an antibacterial function test.

Bamboo can maintain no insects and no mold and rot in the natural environment, because there is a natural antibacterial ingredient "bamboo" in bamboo. Therefore, the bamboo cellulose fiber obtained by the present invention is subjected to natural antibacterial function test and evaluation to test whether it has antibacterial property, and the antibacterial function is evaluated by using Staphylococcus aureus (ATCC 6538P) and Klebsiella pneumoniae (ATCC 4352) as test strains. .

The test results of the antibacterial function according to the above samples 1 to 12 are shown in [Table 2] and [Table 3]. The test method is JIS L1902-1998 quantitative method, and the test strain is Staphylococcus aureus (ATCC 6538P) and pneumonia. Bacillus (ATCC 4352). Among them, the concentration of phytobacteria was 1.0±0.3 E ⁺⁵ (bacteria/ml), indicating that the experiment was effective, Ma=the number of bacteria after scouring immediately after 0 hours of unprocessed samples, and Mb=the number of bacteria after 18-24 hours of unprocessed samples. Mc = number of bacteria after processing for 18-24 hours; bacterial growth activity value = logMb-logMa, bacterial growth activity value > 1.5 means experimentally effective, bacteriostatic value = logMb-logMc, bactericidal value = logMa-logMc; The antibacterial standard of the new functional evaluation protocol (JAFET), the inhibition value of greater than 2.2 indicates that the test sample has antibacterial effect, the sterilization value greater than 0 indicates that the test sample has a bactericidal effect; 1.3 E ⁺⁴ means 13000, and so on.

From the test results of [Table 2] and [Table 3], it is understood that the bamboo cellulose fiber obtained by the present invention has a relatively good antibacterial effect against Staphylococcus aureus and Klebsiella.

Example 4: Deodorization function test was carried out.

The deodorization effect evaluation is based on the ammonia aspiration test as the basis for deodorization. The method is as follows: a certain amount of ammonia gas is charged into a sealed bottle, and the quantitative Lyocell bamboo fiber is placed in the bottle for adsorption for 15 minutes, followed by gas. The gas concentration before and after the insertion of the Lyocell bamboo fiber was measured by a chromatograph (GC), and the deodorizing property was

The results of the ammonia absorption test of each of the above samples are shown in [Table 4].

From the test results of [Table 4], it is understood that the bamboo cellulose fibers obtained by the present invention have a deodorizing function.

Example 5: Negative ion test was performed.

Negative ions, also known as "air vitamins", can produce "negative ions" by means of waterfalls, streams, fountains, fresh oxygen produced by plant photosynthesis, and the sun's ultraviolet rays. Negative ions have the benefits of purifying blood, activating cells, enhancing immunity, adjusting autonomic nerves, and eliminating insomnia, headache, anxiety, and preventing hardening of the blood vessels.

The bamboo cellulose fiber of the present invention is tested for negative ions by using an American digital positive and negative ion tester, an ion counter test method, and manually measuring the number of negative ions by a negative ion analyzer after a certain period of time. The negative ion test results of each sample are shown in [Table 5].

It can be seen from the test results of [Table 5] that the bamboo cellulose fibers obtained by the present invention have a negative ion function, and the number of negative ions in the air is generally about 430 (ions/cc).

Example 6: Antibacterial, deodorizing and negative ion function tests after 10 washes.

Each sample was washed with 5 g/L of washing detergent in hot water at 70 ° C for 10 minutes for 10 minutes, and each of the obtained samples was subjected to functional tests such as antibacterial, deodorizing and negative ions, and the results were as shown in [Table 6] and [Table 7]. 】 and [Table 8].

It can be seen from the test results of [Table 6] and [Table 7] that the bamboo cellulose fiber obtained by the invention has been treated with hot water and detergent for 10 times, and the antibacterial and deodorizing effect of the fiber remains unchanged. The result is about 95%. From the results, it is also shown that the bamboo cellulose fiber obtained by the present invention is a cellulose fiber having a long-acting antibacterial and deodorizing function, and the effect is far superior to that of the surface market. Or an antibacterial fiber to which an antibacterial agent is added; and as a result of the test of [Table 8], the bamboo cellulose fiber obtained by the present invention has an anion effect after being washed 10 times, which is due to the raw material of the bamboo pulp fiber itself. The negative ion property has not been destroyed in the process, so that it has a significant negative ion effect after washing 10 times.

In summary, the bamboo cellulose fiber prepared according to the invention can be applied to textiles, medical and health materials, filter materials, biotechnology materials and photoelectric wafer wiping because of its natural antibacterial, deodorizing and negative ion functions. If the required requirements and uses are indeed an innovative invention with high industrial applicability, the application is made according to law.

Claims (10)

A method for preparing bamboo cellulose fibers having natural antibacterial, deodorizing and anion functions, the steps comprising: a. adding coffee residue to bamboo pulp as a raw material; the waste coffee grounds are firstly passed through a high speed Grinding into micro-particles of 500nm~1000nm (nano) and then adding into the bamboo pulp, the bamboo pulp is selected from bamboo pulp cellulose with α-cellulose content of more than 80%, and the degree of polymerization of the cellulose is referred to as DP. ) between 400 and 800; b. Adding N-methylmorpholine N-oxide (NMMO) and 1,3-phenylene-bis 2-oxazoline (BOX) in the step a bamboo pulp, which is mixed and dissolved into a dope; the waste coffee grounds and bamboo pulp cellulose, oxidized methyl marlin solvent and phenyloxazole additive are used in a horizontal pulping machine. After being placed together, the mixture is pulverized at a high temperature of 60 ° C to 80 ° C, and the oxidized methyl marlin has a high swelling property, high solubility, and fast dissolution rate, thereby achieving rapid mutual mixing and dissolution to form a slurry. (slurry), using a vacuum film evaporator (Thin Film Evaporator, TFE) to 80 Heating at °C~120°C, the water after evaporation and dissolution in 5 minutes is removed to 5~13% to form a dope; c. Dry-Jet Wet Spinning Spinning, after the spinning mucus is squeezed out from the spinning nozzle, and then enters the coagulation bath to solidify and reproduce the yarn; and d. after the solidification and regeneration spinning is subjected to washing, drying, oiling and coiling, etc. , a bamboo fiber having a natural antibacterial, deodorizing and negative ion function of a filament can be obtained. The method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and anion function as described in the first paragraph of the patent application, wherein the content of the waste coffee slag in the bamboo pulp added in the step a is 0.5 wt% to 5 Wt%. The method for producing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions as described in the first aspect of the patent application, wherein the concentration of the oxidized methyl marlin solvent in the step b is 50% to 75%. The method for producing a bamboo cellulose fiber having natural antibacterial, odor suppressing and negative ion functions as described in the first aspect of the patent application, wherein the drying temperature in the step d is from 100 ° C to 150 ° C. The method for producing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions as described in the first paragraph of the patent application, wherein the winding speed in the step d is 200 to 800 meters per minute. The method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions as described in the first paragraph of the patent application, wherein the fiber strength of the bamboo cellulose fiber obtained in the step d is 1.5 g/d to 4.0. g/d. The method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and anion function as described in the first paragraph of the patent application, wherein the fiber elongation rate of the bamboo cellulose fiber obtained in the step d is 4.0% to 8.0%. . For example, the method for preparing bamboo cellulose fibers having natural antibacterial, deodorizing and negative ion functions as described in the first paragraph of the patent application, wherein the fiber-yield coefficient of the bamboo cellulose fibers obtained in the step d is 50 g/d~ 150g/d. For example, the method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions as described in the first paragraph of the patent application, wherein the spinning which is solidified and regenerated in the step d can be washed, dried and oiled. That is, it is cut into staples according to the required length. The method for preparing a bamboo cellulose fiber having natural antibacterial, deodorizing and negative ion functions as described in the first paragraph of the patent application, wherein the solvent recovery step after solidification regeneration and water washing in step d comprises: 1. decolorization: The activated carbon suspension method absorbs and decolorizes, and the non-decolorizing liquid is added with 0.05%~0.10% of activated carbon powder with good adsorption and suspension property, and is alternately treated by blast mixing and adsorption and static suspension adsorption, and the treatment time ratio of the two Decolorization is completed from 1:3 to 1:6 with a treatment time of 8 hours or more. 2. Filtration: It adopts two-stage filtration. The first stage of coarse filtration uses a general filter-type filter to simplify the equipment. However, in order to avoid the accumulation of activated carbon in the outermost layer of the filter element and slow down the filtration speed, the filter aid is pre-clothed. In addition to the surface of the filter element, 0.03%~0.05% is also added to the unfiltered filtrate, so that the filtrate does not have a small amount of bulking filter aid, the filtration speed is greatly improved and can be maintained without any decrease. The filter aid is composed of diatomaceous earth. The ratio of cellulose=4:1 is the best. After the coarse filtration is completed, the residual residue of the residue is centrifuged, dehydrated and recovered, and the filter residue of the filter residue after dehydration still has the filter effect and can be reused once. The second stage of fine filtration uses a precision filter UF. After fine filtration, the filtrate has the same cleanness as the fresh solvent. 3. Concentration: When the process of the invention is recovered by the washing liquid, the solvent concentration needs to be concentrated from 6.5% to 8.0% to 50% to 55%, and the concentration of water per ton of fiber needs to be concentrated and removed by 90 tons, and the concentration load is extremely large; Less time: It adopts three-effect concentration method, and its water removal requires about 0.5 tons of steam per ton. (Although the steam consumption is high, but the power consumption is small); when the fiber output is slightly larger: the MVR concentration method is adopted, and the water removal requires about 0.003~0.03 tons of steam per ton (although the steam consumption is low, but the power consumption is slightly larger) The two kinds of concentration methods are different for different yields, but the concentrated liquid and the condensed water produced can be completely recovered; wherein the concentrated liquid can be used for the solvent of the process; the condensed water can be used for washing the raw silk. 4. Refining: low temperature oxidation and neutralization reduction at 80 °C, using 35% H2O2 as oxidant, 85% N2H4. H2O is a neutralizing reducing agent, and the result of redox determination by potentiometric titration can reduce the NMM content to below 10 ppm, which can improve the purity of NMMO and reduce the loss.