Method for producing multicolored moisture-absorbing exothermic acrylate fiber

Abstract

To provide a method for producing a multicolored moisture-absorbing exothermic acrylate fiber, and a moisture-absorbing exothermic acrylate fiber, in a fiber modification technical field.SOLUTION: A moisture-absorbing exothermic acrylate fiber having different colors can be obtained by semi-crosslinking a plurality of kinds of hydrophilic functional groups on the surface of a polyacrylonitrile fiber using a polymer crosslinking and semi-crosslinking technique on the basis of a chemical modification technique, and subjecting it to chemical reduction and oxidation, and production of a fiber chromophoric group having different colors is controlled, and thereby an effect for stabilizing the color of the fiber can be achieved. The method can greatly improve moisture-absorbing performance and color stability performance of a product after modification, can emit a larger heat quantity after moisture absorption, and can be effectively applied to a moist-heat management field such as coldproof and heat insulation, and moisture absorption and exothermic reaction in winter.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to the field of fiber modification technology, and in particular to a method for producing multicolored moisture-absorbing and heat-generating acrylate fibers. Regarding. [Background technology]

[0002] Moisture-absorbing heat-generating fibers release a large amount of heat by absorbing moisture. It is widely used in thermal insulation products, especially in the fields of clothing and home textiles. There are two main theories about the principle of use. One is to use the strong moisture absorption of the moisture-absorbing heat-generating fiber to absorb air. It captures the highly functional water molecules in the fiber and adsorbs them on the surface of the fiber, thus complying with the law of conservation of energy. According to the study, the kinetic energy of water molecules is converted into thermal energy, achieving the effect of exothermic heating. The other is that the moisture-absorbing and heat-generating fibers absorb the water vapor released by the air and the human body, When water vapor is transformed from gas to liquid, heat is released, achieving the effect of exothermic heating. .

[0003] Moisture absorption and heat generation products not only meet people's need for warmth in winter, but also have aesthetic characteristics. Nowadays, heat-generating fibers are widely used in thermal underwear, sportswear, outdoor clothing, etc. It is widely used in surgical drapes, etc. Currently, the most popular moisture-absorbing and heat-generating fiber is moisture-absorbing and heat-generating viscose. They are divided into three categories: fiber, moisture-absorbing heat-generating acrylate fiber, and composite moisture-absorbing heat-generating fiber. Of all moisture absorbing and heat generating fibers, acrylate fibers have the following characteristics: moisture absorption, water absorption, and heat generation. It has obvious advantages in several aspects such as durability and durability, and is the most popular moisture absorbing heat generating product at present. It is widely used.

[0004] Currently, there are many moisture absorbing heat generating acrylate fibers on the market, such as Mizuno Corporation's Breathe. Thermo, Toyobo Co., Ltd.'s Moisture Care and Toho Boshoku Co., Ltd.'s S All unburners are chemically modified polyacrylonitrile fibers with amine reagents and amines. The crosslinking and hydrolysis of alkali converts the nitrile groups in the polyacrylonitrile fibers into Converts to hydrophilic groups such as amide groups, carboxyl groups, and carboxyl metal salts, and improves moisture absorption of fibers. Its performance has been greatly improved, and it can release a large amount of heat by absorbing moisture and water vapor. However, most of the moisture-absorbing heat-generating acrylate fibers on the market today are red in color, and There are problems with color inconsistencies between different batches of products and color deepening over time. In 2014, Mizuno Corporation announced that it had developed a fluorescent enhancer The whitening agent is used to modify the Breath Thermo moisture absorbing heat generating acrylate fiber, resulting in a red color. However, the use of fluorescent agents has a negative impact on the safety of the product. also had a certain influence.

[0005] Therefore, how to further solve the color problem of moisture-absorbing heat-generating acrylate fiber, The problem of expanding the application of the fiber in the field of use is still in the field of moisture absorption and heat generation products. This is an important problem that needs to be urgently solved. Summary of the Invention [Problem to be solved by the invention]

[0006] However, currently, most of the moisture absorbing heat generating acrylate fibers on the market are red in color. In addition, there is a problem that the color of products from different batches does not match, and the color deepens over time. This affects the stability of the product, and the existing red color has been reduced to white. The moisture-absorbing heat-generating acrylate fiber product with improved color tone uses fluorescent agents, so the use of the product This will have a certain impact on the safety performance of the vehicle.

[0007] The present invention is based on chemical modification technology and uses polymer crosslinking and semi-crosslinking technology to The hydrophilic functional groups of the polyacrylonitrile fibers are semi-crosslinked on the surface of the fibers, and are then chemically reduced, acidified, and then bonded to the fibers. After the polymerization process, the acrylate fiber with moisture absorption and heat generation function is obtained. The present invention aims to provide a rate fiber and a manufacturing method thereof. By controlling the reaction time, reaction temperature, types of reagents, and material mixing ratios, Colored moisture absorbing heat generating acrylate fibers can be obtained, the colors being white, cream, beige, etc. The present invention provides the following color by the antioxidant fixation treatment: It can control the generation of different color fiber chromophores and achieve the effect of stabilizing the fiber color. The present invention provides a method for greatly simplifying the manufacturing process, and thus allows for rapid industrialization. It is easy to produce, and the moisture absorption and color stability of the modified product are greatly improved, and the After getting wet, it can release more heat, making it more useful in areas such as winter cold protection and heat generation through moisture absorption. It can be applied effectively. [Means for solving the problem]

[0008] 1. The white moisture-absorbing heat-generating acrylate fiber described in this invention is made by a short-time two-bath molding method using polyacrylate. The lylonitrile fiber is modified to obtain a white moisture-absorbing heat-generating acrylate fiber, and the fiber absorbs water molecules. It is characterized by its ability to release a large amount of heat after absorbing and adsorbing.

[0009] In order to achieve the above objectives, the present invention provides the following technical solutions: The present invention provides a method for producing a white moisture-absorbing and heat-generating acrylate fiber, Polyacrylonitrile fiber is mixed with a mixed solution of a crosslinking agent and an antioxidant to cause a chemical crosslinking reaction. to obtain crosslinked modified polyacrylonitrile fibers; The crosslinked modified polyacrylonitrile fiber is mixed with a mixed solution of an alkaline solution and an antioxidant. Then, an alkaline hydrolysis reaction is carried out to obtain a hydrolysis-modified moisture-absorbing heat-generating acrylate fiber. and

[0010] Preferably, the polyacrylonitrile fiber has a white color and a fineness of 1.2 to 15D. The length is 32 to 64 mm.

[0011] Preferably, the crosslinking agent in the crosslinking agent solution is polyethylene, ethylenediamine, poly Vinylamine chloride, propanediamine, acrylic acid, polyacrylic acid, ethylene glycol or glycerin, The concentration of the crosslinking agent in the crosslinking agent solution is 0.5 to 2.5 mol / L.

[0012] Preferably, the alkaline solution is ammonia water, sodium hydroxide solution, potassium hydroxide. solution, magnesium hydroxide solution, calcium hydroxide solution; The concentration of the alkaline solution is 2 to 4 mol / L.

[0013] Preferably, the antioxidant is calcium ascorbate; The concentration of the antioxidant is 1 mol / L.

[0014] Preferably, the temperature of the chemical crosslinking reaction is 115 to 125° C., and the time is 0.5 to 1 hour.

[0015] Preferably, the crosslinked modified polyacrylonitrile fiber is white in color.

[0016] Preferably, the alkaline hydrolysis reaction is carried out at a temperature of 125° C. for a period of 0.5 to 1 hour. .

[0017] Preferably, the hydrolytically modified acrylate fibers are white in color.

[0018] 2. The cream, beige or yellow moisture absorbing and exothermic acrylate fiber according to the present invention is short Polyacrylonitrile fiber is modified by a two-bath molding process for 1 hour to produce cream, beige or yellow color. After obtaining the moisture-absorbing heat-generating acrylate fiber, the fiber absorbs and adsorbs water molecules, and then generates a large amount of heat. It is characterized by its ability to be released.

[0019] In order to achieve the above objectives, the present invention provides the following technical solutions: The present invention provides a method for producing cream, beige or yellow moisture absorbing and heat generating acrylate fibers. death, Polyacrylonitrile fiber is mixed with a crosslinking agent and an alkaline solution to form a chemical crosslinking reaction. reaction and alkaline hydrolysis reaction, then anti-oxidation fixing treatment, and moisture-absorbing heat-generating acrylate obtaining fibers, Preferably, the polyacrylonitrile fiber has a white color, a fineness of 1.2 to 15D, and a length of is 32 to 64 mm.

[0020] Preferably, the crosslinking agent in the crosslinking agent solution is polyethylene, ethylenediamine, poly Vinylamine chloride, propanediamine, hydrazine hydrate, acrylic acid, polyacrylic acid , ethylene glycol, or glycerin; The concentration of the crosslinking agent in the crosslinking agent solution is 0.5 to 2.5 mol / L.

[0021] Preferably, the alkaline solution is ammonia water, sodium hydroxide solution, potassium hydroxide. solution, magnesium hydroxide solution, calcium hydroxide solution; The concentration of the alkaline solution is 2 to 4 mol / L.

[0022] Preferably, the temperature of the chemical reaction is 115 to 125° C., and the time is 1 to 4 hours.

[0023] Preferably, the antioxidant fixing treatment is carried out by treating the produced fibers with an antioxidant solution. be.

[0024] The concentration of the antioxidant solution was 1 mol / L, the solvent was water, the treatment temperature was 65° C., and the treatment time was 0.5 h.

[0025] 3. The orange, red, reddish purple or brown moisture absorbing and exothermic acrylate fiber according to the present invention can be used for a long time. The polyacrylonitrile fiber was modified by the three-bath molding method, and then the fiber was subjected to an antioxidant fixing treatment. The resulting hygroscopic heat-generating acrylate fiber is orange, red, reddish purple, or brown. It is characterized by its ability to release a large amount of heat after absorbing and adsorbing.

[0026] In order to achieve the above objectives, the present invention provides the following technical solutions: The present invention provides a method for producing an orange, red, magenta or brown hygroscopic heat-generating acrylate fiber modification. death, Polyacrylonitrile fiber is mixed with a crosslinking agent and an alkaline solution to form a chemical crosslinking reaction. and performing a hydrolysis reaction to obtain an orange moisture-absorbing heat-generating acrylate fiber. The orange moisture-absorbing heat-generating acrylate fiber is mixed with an oxidizing agent solution, and the fiber is subjected to an oxidation treatment. and obtaining red, magenta or brown moisture-absorbing heat-generating acrylate fibers.

[0027] Preferably, the polyacrylonitrile fiber has a white color, a fineness of 1.2 to 15D, and a length of is 32 to 64 mm.

[0028] Preferably, the crosslinking agent in the crosslinking agent solution is polyethylene, ethylenediamine, poly Vinylamine chloride, propanediamine, hydrazine hydrate, acrylic acid, polyacrylic acid , ethylene glycol, or glycerin; The concentration of the crosslinking agent in the crosslinking agent solution is 0.5 to 2.5 mol / L.

[0029] Preferably, the alkaline solution is ammonia water, sodium hydroxide solution, potassium hydroxide. solution, magnesium hydroxide solution, calcium hydroxide solution; The concentration of the alkaline solution is 2 to 4 mol / L.

[0030] Preferably, the chemical crosslinking and hydrolysis reaction is carried out at a temperature of 115 to 125° C. for 1 to 4 hours. be.

[0031] Preferably, the oxidizing agent in the oxidizing agent solution is concentrated sulfuric acid, nitric acid, ammonium persulfate, or One or more of potassium manganate and sodium hypochlorite.

[0032] The concentration of the oxidant solution is 0.5 to 11.5 mol / L; Preferably, the temperature of the oxidation reaction is 85 to 125° C., and the time is 1 to 1.5 hours.

[0033] Preferably, the antioxidant fixing treatment is carried out by treating the produced fibers with an antioxidant solution. be.

[0034] The concentration of the antioxidant solution was 1 mol / L, the solvent was water, the treatment temperature was 65° C., and the treatment time was 0.5 h. Effect of the Invention

[0035] This invention is based on chemical modification technology and aims to modify the basic structure of polyacrylonitrile fiber to various degrees. By changing the temperature and using polymer cross-linking and semi-cross-linking techniques, multiple hydrophilic functionalities can be obtained. The groups are semi-crosslinked on the surface of polyacrylonitrile fibers, and after chemical reduction and oxidation processes, The present invention provides a method for producing a moisture-absorbing and heat-generating modified polyacrylonitrile fiber having a plurality of warm colors. The manufacturing method provided by the present invention is characterized in that the reaction is carried out by strictly controlling the process and technical conditions. Various chromophores such as imide groups, amide groups, carboxyl groups, and carboxylates formed in the By controlling the content of auxochromes, the effect of controlling the color of the fiber very precisely can be achieved, and the current market Various problems caused by the color of the acrylate fiber, such as multi-lot The color of the textile products in the sample does not match, the color changes over time, and the reagents used contain fluorescent agents. The fiber can effectively solve various problems such as the inclusion of It has multiple functions such as color, excellent super moisture absorption, moisture absorption heat generation, deodorization, etc., and is suitable for various application fields. Can be adapted to. [Brief description of the drawings]

[0036] [Figure 1] Schematic diagram of the structural changes during the crosslinking reaction. [Diagram 2] Schematic diagram of structural changes during alkaline hydrolysis reaction. [Diagram 3] Moisture absorption and heat generation temperature rise curve of multi-colored moisture absorbing and heat generating acrylate fiber. [Figure 4] Detection of deodorizing performance of multi-color moisture absorbing and heat generating acrylate fiber. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] The present invention is based on the following concept: Unmodified acrylic fibers are white in color; After cross-linking modification and hydrolysis reaction, the fibers turn cream, beige or yellow in color and become more pigmented over time. The inventors have found that the red color gradually appears in air over time. The color change is mainly due to the color-developing or auxiliary coloring functionalities such as nitrogen-containing and oxygen-containing functionalities that are generated during the fiber modification. groups, such as imide groups, amide groups, carboxyl groups, carboxylates, etc. The formation of these functional groups absorbs ultraviolet or visible light due to electronic transition effects. Furthermore, a red shift in the absorption peak in the ultraviolet-visible absorption spectrum (UV) occurs. The wavelength of the light absorption peak shifts to longer wavelengths, and the light absorption wavelength gradually decreases from 435 nm. The wavelength of light gradually changes to 750 nm, producing a color change that is visible to the human eye. After studying the theory, the present invention has been developed to efficiently and stably produce multi-color moisture absorbing heat generating acrylate fibers. The present invention provides a method for producing the fiber, which is available in a variety of colors and has excellent properties such as super moisture absorption, moisture absorption heat generation, deodorization, etc. It has multiple functions and can be widely used in spinning and weaving technology, clothing, home textiles, etc. This solves the annoying problem of color issues in the field.

[0038] The multicolor moisture absorbing and heat generating acrylate fiber according to the present invention will be described in detail below.

[0039] The main reason for the color change produced by the multicolor moisture-absorbing heat-generating acrylate fiber described in this invention is The reason is that different types and degrees of chemical reactions take place, and the imide groups, The chromophores or auxophores such as amide groups, carboxyl groups, and carboxylates are generated, and these functional groups are Under the comprehensive effect of the group, the light absorption peak wavelength of the fiber material gradually changes from 435nm to 750nm. m, and the color gradually changes from white to red. During fiber modification, the antioxidant is added. By using this method, the oxidative conversion of functional groups in the fibers can be effectively inhibited, thereby preventing the color change of the fibers. This effectively suppresses oxidation.

[0040] The moisture-absorbing heat-generating acrylate fiber according to the present invention undergoes the following structural changes during the crosslinking reaction: Under heating conditions, the addition of external energy changes the molecular structure inside the polyacrylonitrile fiber. The addition of a cross-linking agent can break down the dense structure of the chains, and at the same time, the addition of a cross-linking agent can break down the two adjacent molecular chains. The bridge structure can be connected, and the degree of swelling during alkaline hydrolysis can be reduced. The reactive crosslinking agent undergoes a crosslinking reaction and at the same time undergoes a certain degree of hydrolysis and oxidation reaction. It reacts with the nitrile groups on the fiber polymer chain to generate imide groups, amide groups, carboxyl groups, etc. forming a chromophore or auxophore, which in turn produces a red shift in the optical absorption peak of the overall fiber; Depending on the degree of reaction, the wavelength of the light absorption peak is 350 to 480 nm. The fibres may be cream, beige or yellow in colour.

[0041] The moisture absorbing heat generating acrylate fiber according to the present invention undergoes the following structural changes during the hydrolysis reaction: The hydrolysis reaction that occurs in this process for polyacrylonitrile fibers is mainly The reaction of the nitrile groups in the fiber polymer chain with an alkaline solution. Usually, the nitrile groups are When it reacts with alkali at high temperature, the carbon-nitrogen triple bond of the nitrile group opens and reacts with alkali to form First, an amide group is formed, and then as the reaction proceeds, the amide group is converted to a carboxyl group. , and then hydrolyzed to carboxylate, and after that, due to the extremely strong hydrophilicity and swelling properties of both, Part of the fiber is decomposed in the alkaline solution, and at the same time the fiber becomes gel-like and slippery. However, after the cross-linking reaction, the polymer chains adjacent to each other are formed. The crosslinked structure can effectively increase the alkali resistance stability of the fiber, and the crosslinked modified poly When acrylonitrile fiber undergoes a hydrolysis reaction with alkali, only a very small amount of ion is released. The amide groups were oxidized to carbon-oxygen double bonds, and many of the nitriles that had not undergone other crosslinking reactions were In this process, the alkyl group reacts with the alkali to form an amide group, a carboxyl group, or a carboxyl group. At the same time, carbon atoms such as amide groups, carboxyl groups, or carboxylates are generated. As the double bond-containing chromophores are generated, the optical absorption peak of the fiber is red-shifted and the long The wavelength continues to move in the direction of wavelength, gradually increasing from 435-480 nm to 480-500 nm. The color gradually changes from beige to red.

[0042] The moisture-absorbing heat-generating acrylate fiber according to the present invention undergoes the following structural changes during the oxidation reaction: Polyacrylonitrile fibers are converted to acrylate fibers after crosslinking and hydrolysis modification. The nitrile group, which is the original characteristic group of the fiber, can be converted into an amino group, an amide group, a carboxyl group or a carboxyl group. At the same time, the color of the fiber changes from the original white to orange or red. The color of the fiber continues to change toward red over time, which is due to the fact that the fiber is In the fiber polymer chain, there are many imide groups remaining after the carbon-nitrogen triple bond of the nitrile group is opened. The imide group is converted into a carbon-oxygen double bond under the effect of long-term air oxidation, and the optical absorption peak This changes the wavelength of the light emitted by the fiber, moving it towards longer wavelengths and making the red color of the fiber more prominent. It is.

[0043] The present invention provides a method for producing a multi-color moisture absorbing and heat generating acrylate fiber, Polyacrylonitrile fibers are mixed with a crosslinking agent or a mixed solution of a crosslinking agent and an antioxidant, and the resulting mixture is then chemically treated. and carrying out a chemical crosslinking reaction to obtain crosslinked modified polyacrylonitrile fibers. The color of the acrylonitrile fiber is white, the fineness is preferably 1.2 to 15D, and the length is preferably In the present invention, the concentration of the crosslinking agent in the crosslinking agent solution is preferably or 0.5 to 2.5 mol / L, more preferably 0.8 to 1.5 mol / L, and most preferably In the present invention, the crosslinking agent solution has a crosslinking concentration of 0.9 to 1.1 mol / L. The agent is preferably polyethylene, ethylenediamine, polyvinyl chloride amine, propane Diamine, hydrazine hydrate, acrylic acid, polyacrylic acid, ethylene glycol or glycol and the crosslinker comprises one or more of the above specific selections. In the above case, the present invention does not have any special limitations on the blending ratio of the specific materials. In the present invention, the solvent in the crosslinking agent solution is Preferably, the solvent is water and / or ethanol. When the solvent is water and ethanol, the present The present invention does not have any particular limitation on the ratio of the amounts of water and ethanol used, and any In the present invention, the polyacrylonitrile fiber and the crosslinking agent are mixed in a mixing ratio. The mass ratio of the crosslinking agent in the liquid is preferably (7-1):(1-3), more preferably (4. In the present invention, the ratio is preferably (5-1):(1-1.5), and more preferably (2-1):1. The temperature of the chemical crosslinking reaction is preferably 115 to 125°C, more preferably 117 to 123°C. The most preferred temperature is 119 to 121° C., and the preferred time is 0.5 to 2 hours. The antioxidant is calcium ascorbate, and the concentration in the mixed solution is 1. The present invention does not have any particular limitations on the mixing process, Processes well known to those skilled in the art may be used.

[0044] The crosslinked modified polyacrylonitrile fiber and an alkaline solution or an alkaline solution and an antioxidant The mixture is mixed and subjected to an alkaline hydrolysis reaction to obtain hydrolyzed modified acrylate fibers. In the present invention, the alkaline solution is preferably ammonia water, sodium hydroxide, solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution The concentration of the alkaline solution is preferably 2 to 4 mol / L, more preferably The concentration is preferably 2.5 to 3.5 mol / L, and most preferably 2.8 to 3.2 mol / L. In the present invention, the crosslinked modified polyacrylonitrile fiber and the alkali in the alkaline solution The mass ratio of these is preferably (3-1):(1-2), more preferably (1.5-1):(1- 1.5), and most preferably (1.2 to 1):1. The temperature of the hydrolysis reaction is preferably 125° C., and the time is preferably 1.5 to 4 hours, more preferably The time is preferably 1.6 to 1.9 hours, and most preferably 1.7 to 1.8 hours. The antioxidant is calcium ascorbate, and its concentration in the mixed solution is 1 mo In the present invention, the color of the hydrolysis modified acrylate fiber is preferably white. The present invention provides a method for mixing the mixture in the following manner: There are no particular limitations and any process well known by a person skilled in the art may be used.

[0045] The modified hydrolyzed acrylate fiber is mixed with an oxidizing agent solution to carry out an oxidation reaction; In the present invention, the concentration of the oxidizing agent solution is preferably 0.5 to 11.5 mol / L, more preferably 3 to 10 mol / L, and most preferably 5 to In the present invention, the oxidizing agent in the oxidizing agent solution is preferably concentrated. Sulfuric acid, nitric acid, ammonium persulfate, potassium permanganate and sodium hypochlorite and the oxidizing agent is one or more of the above specific selections. In this case, the present invention is not limited to any particular ratio of the specific substances, and may be any ratio. In the present invention, the modified hydrolyzed acrylate fiber and The mass ratio of the oxidizing agent in the oxidizing agent solution is preferably (3 to 1):(1 to 11), more preferably The ratio is preferably 1:(1-10), and most preferably 1:(2-4). There is no particular limitation on the process, and the process is well known by those skilled in the art. In the present invention, the temperature of the oxidation reaction is preferably 85 to 125° C. The temperature is more preferably 95 to 115°C, and most preferably 100 to 110°C. The time is preferably After the oxidation reaction is completed, the reaction time is 1 to 1.5 hours, and more preferably 1 to 1.2 hours. The method also preferably includes sequential washing and drying, and the present invention relates to said washing and drying process. There are no particular limitations on the process, and the process may be carried out using processes well known to those skilled in the art. The color of the moisture absorbing heat generating acrylate fiber after oxidation is orange, red, reddish purple or brown. It is color.

[0046] The multi-color moisture absorbing and heat generating acrylate fiber described in the present invention is a fiber that has undergone the above-mentioned multiple complex chemical modification processes. The modified fiber has excellent moisture absorption and water absorption properties and is stable at 20℃ × 65% RH. Under environmental conditions, the moisture absorption performance can reach 21-42%. The multicolored moisture absorbing heat generating acrylate fiber can produce a remarkable moisture absorbing heat generating effect within 10 seconds. The maximum temperature after wet heating can reach 42.2℃.

[0047] The multi-color moisture absorbing and heat generating acrylate fiber described in the present invention is a fiber that has undergone the above-mentioned multiple complex chemical modification processes. The fiber surface has many fine pores after modification, which effectively absorbs unpleasant odors in the air. After modification, the fiber material can react with acid and alkali to some extent. Therefore, it has excellent deodorizing and odor eliminating properties.

[0048] The multi-colored moisture absorbing and heat generating acrylate fiber according to the present invention may be used alone or in combination with other types of Used together with fiber raw materials such as natural fibers, organic fibers, man-made fibers, regenerated fibers, inorganic fibers, etc. According to different needs and applications, different colors of moisture absorbing heat generating acrylate fiber can be used. can be selected to use different raw material blend ratios.

[0049] For example, the multi-color moisture absorbing and heat generating acrylate fiber described in the present invention can be made of cotton, linen, silk, wool, rayon, etc. It can be blended with fibers such as cellulose, Tencel, cupra, polyester, or nylon to produce yarn, The moisture absorbing heat generating acrylate fiber content is 5-90%, cotton, linen, silk, wool, rayon, The fiber content of the material is 10 to 95%. Yarn made from multicolor moisture absorbing heat generating acrylate fibers is vortex spun and ring spun. It can be produced by conventional spinning methods such as silo spinning, silo spinning, or compact silo spinning. The yarn is a composite yarn of a type in which a plurality of types of fibers are arranged in parallel, and the multi-color moisture absorbing heat generating material in the yarn is The acrylate fiber content is 10% or more, which means it has outstanding moisture absorption and heat generation effects and deodorizing and deodorizing effects. It has the effect of heating the maximum temperature up to 8.8℃, and the deodorizing effect is 98%. The multi-color moisture absorbing and exothermic acrylate fiber according to the present invention is characterized by the above. , silk, wool, rayon, Tencel, cupra, polyester or nylon, and other fibers. After the processes of joining, carding, wrapping, setting, etc., hollow cotton flock is produced, where Moisture absorbing heat generating acrylate fiber content: 5-90%, cotton, linen, silk, wool, rayon, Tencel The content of fibers such as cupra, polyester or nylon is 10 to 95%. The hollow cotton flock made of the moisture absorbing heat generating acrylate fiber is made of polyester wadding. Manufactured with adhesive-free cotton, PrimaLoft, needle punched cotton, or spunlace cotton. The hollow cotton flock can be a composite hollow cotton flock in which a plurality of types of fibers are uniformly mixed. The content of moisture-absorbing heat-generating acrylate fiber in the hollow cotton flock is 10% or less. That is, it has a remarkable moisture absorption and heat generation effect and a deodorizing and deodorizing effect. It can reach a temperature of 2.4℃ and has a deodorizing effect of over 97%.

[0050] The multi-color moisture absorbing and heat generating acrylate fiber product according to the present invention can be applied to clothing products. For example: underwear, undergarments, shirts, T-shirts, jumpers, sweaters, pants, jackets , windbreaker, hanten, jacket, hat, earmuffs, scarf, gloves, socks, shoulder Supporters, arm warmers, leg warmers, belly warmers, elbow pads, masks, tie It is Tsu.

[0051] The multi-color moisture absorbing and heat generating acrylate fiber product according to the present invention is suitable for home textile products. Applications include: futons, quilts, mattresses, pillows, mattress pads, pillow pads, quilts Covers, underlay covers, pillow covers, multi-purpose covers, cushions, carpets, rugs, sofas - Covers, kotatsu, blankets, pet beds, slippers, room shoes, sleeping bags, fur It consists of a cloth, a floor blanket, a lap blanket, and a towel blanket.

[0052] Example 1 20 g of polyacrylonitrile fiber (white in color, 1.2D fineness, 38 mm in length) 200 mL of a mixed solution of ethylenediamine and calcium ascorbate (solvent: water, ethylenediamine, calcium ascorbate) The concentration of ethylenediamine is 0.5 mol / L, and the concentration of calcium ascorbate is 1 mol / L) and a chemical crosslinking reaction was carried out (the temperature of the chemical crosslinking reaction was 115°C, and the time was 1 hour). The crosslinked modified polyacrylonitrile fiber is obtained, 20 g of the crosslinked modified polyacrylonitrile fiber was added to 200 mL of 2 mol / L agarose solution. A mixture of ammonia water and 1 mol / L calcium ascorbate (solvent: water, ammonia) The concentration of calcium ascorbate was 1 mol / L. Then, alkaline hydrolysis reaction (temperature: 115℃, time: 1h) was carried out, and white hygroscopic exothermic alkoxide was obtained. Relate fiber (white in color, moisture content reaches 21.4%, and the fiber after absorbing moisture has a significant heat capacity. The temperature after absorbing moisture and generating heat reached a maximum of 34.5°C.

[0053] Example 2 20g of polyacrylonitrile fiber (white in color, 3.3D fineness, 51mm in length) 200 mL of a mixed solution of ethylenediamine and aqueous ammonia (solvent: water, ethylenediamine The concentration of ammonium hydroxide was 1 mol / L and the concentration of ammonia water was 2 mol / L. An alkaline hydrolysis reaction is carried out (the temperature of the chemical reaction is 120°C, and the time is 1 hour), and then the preparation The fibers were then placed in an antioxidant solution (water as the solvent, calcium ascorbate as the antioxidant, concentrated The concentration was 1 mol / L, and antioxidant fixation treatment was performed (treatment temperature: 65°C, time: 0.5 h), moisture absorbing heat generating acrylate fiber (cream color, moisture content reaches 23.2%, moisture absorbing After absorbing water, the fiber can release significant heat, and the temperature after absorbing moisture can reach a maximum of 35.7℃. Got it.

[0054] Example 3 20g of polyacrylonitrile fiber (white in color, 3.3D fineness, 51mm in length) 200 mL of a mixed solution of ethylenediamine and aqueous ammonia (solvent: water, ethylenediamine The concentration of ammonium hydroxide was 2 mol / L and the concentration of ammonia water was 2 mol / L. An alkaline hydrolysis reaction is carried out (the temperature of the chemical reaction is 120°C, and the time is 1.5 hours), and then The produced fiber is then soaked in an antioxidant solution (water is the solvent, calcium ascorbate is the antioxidant). The concentration was 1 mol / L) and antioxidant fixation treatment was performed (treatment temperature was 65°C, time was 0 The moisture-absorbing heat-generating acrylate fiber (yellow in color, moisture content reached 23.8%) was then absorbed. After absorbing moisture, the fiber can release significant heat, and the temperature after absorbing moisture can reach a maximum of 35.9℃. ) was obtained.

[0055] Example 4 20g of polyacrylonitrile fiber (white in color, 5.5D fineness, 64mm in length) 200 mL of a mixed solution of hydrazine hydrate and aqueous ammonia (solvent is water, hydrazine hydrate The concentration of ammonia water was 1 mol / L, and the concentration of ammonia water was 4 mol / L. Potash hydrolysis reaction is carried out (the temperature of the chemical reaction is 120°C, the time is 2 hours), and then the fibers are 200 mL of ammonium persulfate solution (solvent is water, concentration of ammonium persulfate is 0.5 mol / L) and carry out an oxidation reaction (the temperature of the oxidation reaction is 115°C, and the time is 1 hour). Next, the produced fiber is put into an antioxidant solution (the solvent is water, and the antioxidant is calcium ascorbate). The concentration of sodium was 1 mol / L, and antioxidant fixation treatment was performed (treatment temperature: 65°C, time: The time between the drying and drying is 0.5 hours. The moisture absorbing heat generating acrylate fiber (orange in color, moisture content reaches 24.3%) After absorbing moisture, the fibers can release significant heat, and the temperature after absorbing moisture can reach a maximum of 37.8°C. achieved).

[0056] Example 5 20g of polyacrylonitrile fiber (white in color, 5.5D fineness, 64mm in length) 200 mL of a mixture of hydrazine hydrate and sodium chloride (solvent: water, hydrazine hydrate) The concentration of sodium hydroxide was 2 mol / L) and chemical crosslinking was performed. and then carrying out an alkaline hydrolysis reaction (the temperature of the chemical reaction is 125°C, and the time is 2 hours), and then The fibers were placed in 200 mL of potassium permanganate solution (solvent: water, concentrated potassium permanganate). The oxidation reaction was carried out at a temperature of 115°C and for a time of 2 mol / L. 1h), and then the produced fibers were soaked in an antioxidant solution (the solvent was water, and the antioxidant was ascorbic acid). The calcium hydroxide was added to the water to perform antioxidant fixation treatment (treatment temperature: 65 ℃, time 0.5h), and moisture-absorbing heat-generating acrylate fiber (color is red, moisture content is 25. After absorbing moisture, the fiber can release significant heat, and the temperature after absorbing moisture can reach a maximum of 38 The temperature reached 0.7°C.

[0057] Example 6 20g of polyacrylonitrile fiber (white in color, 7D fineness, 64mm in length) was 00mL of a mixed solution of hydrazine hydrate and sodium chloride (solvent is water, concentration of hydrazine hydrate is The concentration of sodium hydroxide was 3 mol / L and the concentration of sodium hydroxide was 2 mol / L. Potash hydrolysis reaction is carried out (the temperature of the chemical reaction is 125°C, the time is 3 hours), and then the fibers are 200 mL of potassium permanganate solution (solvent is water, concentration of potassium permanganate is 4 mM) ol / L) and carry out an oxidation reaction (the temperature of the oxidation reaction is 125°C, and the time is 1.5 hours). ), and then the produced fiber is soaked in an antioxidant solution (the solvent is water, and the antioxidant is calcium ascorbic acid). Calcium, concentration 1 mol / L) was added to the water and antioxidant fixation treatment was performed (treatment temperature 65°C, Time: 0.5h), moisture absorbing heat generating acrylate fiber (color: reddish purple, moisture content: 28.4%) After absorbing moisture, the fibers can release significant heat, and the temperature after absorbing moisture can reach a maximum of 39.6℃. (obtained).

[0058] Example 7 20g of polyacrylonitrile fiber (white in color, 15D fineness, 64mm in length) 200mL of a mixture of hydrazine hydrate and sodium chloride (solvent is water, concentrated hydrazine hydrate) The concentration of sodium hydroxide was 4 mol / L and the concentration of 2.5 mol / L was added to the Then, the alkaline hydrolysis reaction was carried out (the temperature of the chemical reaction was 125°C, and the time was 4 hours), and then the fibers were The fibers were added to 200 mL of sulfuric acid solution (solvent: water, sulfuric acid solution concentration: 11.5 mol / L). Then, an oxidation reaction was carried out (the temperature of the oxidation reaction was 125° C., and the time was 1.5 hours). The fibers were then placed in an antioxidant solution (solvent: water, antioxidant: calcium ascorbate, concentration: 1mol / L) and antioxidant fixation treatment was performed (treatment temperature: 65℃, time: 0.5h). , Moisture-absorbing heat-generating acrylate fiber (brown in color, moisture content reaches 42%), after absorbing moisture, It was possible to release a significant amount of heat, and the temperature after absorbing moisture reached a maximum of 44.2°C.

[0059] The above is merely a preferred embodiment of the present invention, and it is understood that those skilled in the art may deviate from the principles of the present invention. Without any modification, multiple improvements and embellishments can be made, and these improvements and embellishments are also protected by the present invention. It should be within the range.

Claims

1. A method for producing multi-color moisture absorbing heat generating acrylate fibers, using polyacrylonitrile fibers as raw materials. As a material, after cross-linking reaction, alkaline hydrolysis reaction oxidation reaction and antioxidant fixing treatment, different colors can be obtained. A method for producing a multicolor moisture absorbing and heat generating acrylate fiber.

2. In the crosslinking reaction, the polyacrylonitrile fiber is reacted with a crosslinking agent to form a crosslinked modified polyacrylonitrile fiber. The crosslinking agent is ethylene, ethylenediamine, poly(ethylene glycol), tert-butyl ether, ... Vinylamine chloride, propanediamine, hydrazine hydrate, acrylic acid, polyacrylic acid The solvent is one or more of ethylene glycol or glycerin. The method of claim 1.

3. The alkaline hydrolysis reaction is a reaction of modified polyacrylonitrile fiber with an alkaline solution. to obtain hydrolyzed modified acrylate fibers, the alkaline solution being ammonia Water, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution or calcium hydroxide solution 2. The method according to claim 1, wherein the solution is one or more of a calcium solution. 。

4. The oxidation reaction is a reaction between hydrolyzed modified acrylate fibers and an oxidizing agent to produce a multi-color system. The object is to obtain a moisture-absorbing heat-generating acrylate fiber, and the oxidizing agent is concentrated sulfuric acid, nitric acid, ammonium persulfate, etc. One or more of the following: monium, potassium permanganate, or sodium hypochlorite. The method according to claim 1,

5. The antioxidant fixing treatment is a process in which an antioxidant is used to treat the fibers, thereby preventing oxidation of the fibers. The object of the present invention is to prevent discoloration of the fibers due to further oxidative conversion of the nitrogen-containing groups, 2. The method according to claim 1, wherein the antioxidant is calcium ascorbate. Law.

6. The colors of the multi-color moisture absorbing heat generating acrylate fiber are white, cream, beige, yellow.

6. The method according to claim 1, wherein the color of the ink is one of orange, red, reddish purple, and brown.

3. The multicolor moisture-absorbing and heat-generating acrylate fiber according to claim 1 .

7. The color change of the multicolored moisture absorbing heat generating acrylate fiber is mainly caused by the inside of the fiber. The imide group, amide group, carboxyl group, carboxylate salt, and other chromophores or auxophores The method provided by the present invention is particularly advantageous in that it allows precise control over the fixation of the color of the fibers. A change in color of the fiber according to any one of claims 5 to 6.

8. The multicolored moisture absorbing and heat generating acrylate fiber has excellent moisture absorbing and water absorbing properties, moisture absorbing and heat generating properties, and deodorizing properties. The product according to any one of claims 1 to 5, characterized in that it has multiple functions such as deodorizing properties. Construction method.

9. The multi-color moisture absorbing and heat generating acrylate fiber can be applied to various situations depending on the color and specifications.

8. The multi-color moisture absorbing and heat generating acrylate fiber according to claim 7.

10. The multi-color moisture absorbing and exothermic acrylate fiber can be used in various types of yarns, knits, woven fabrics, nonwoven fabrics, and medium-sized fabrics. The fiber structure can be applied to textile products such as hollow cotton flock, and the textile products include clothing products, bedding products, The multi-color moisture absorbing heat generating acrylate according to claim 8, which can be used for furniture and the like. Fiber.

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