Method for manufacturing multi-colored moisture-absorbing, heat-generating acrylate fibers

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

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[0001] The present invention relates to the field of fiber modification technology, and particularly to a method for manufacturing multi-color moisture-absorbing and heat-generating acrylate fibers thereof.

Background Art

[0002] Moisture-absorbing and heat-generating fibers release a large amount of heat due to moisture absorption. Currently, they are already widely used in thermal insulation products in autumn and winter , particularly in the fields of clothing and home textiles. There are two mainstream claims regarding the working principle of moisture-absorbing and heat-generating fibers. One is to utilize the strong moisture absorption of moisture-absorbing and heat-generating fibers to capture high-functional water molecules in the air, adsorb them on the surface of the fibers, and according to the law of conservation of energy , the kinetic energy of water molecules is converted into thermal energy to achieve the effect of heat generation . The other is that moisture-absorbing and heat-generating fibers absorb the water vapor released by the air and the human body, and when the water vapor is converted from a gas to a liquid, heat is released to achieve the effect of heat generation . .

[0003] Moisture-absorbing and heat-generating products not only meet people's needs for warmth in winter but also have aesthetic features and are becoming increasingly popular among people. Currently, heat-generating fibers are widely used in thermal underwear, sportswear, outdoor clothing , surgical drapes, etc. Currently, moisture-absorbing and heat-generating fibers can be divided into three categories: moisture-absorbing and heat-generating viscose fibers , moisture-absorbing and heat-generating acrylate fibers, and composite moisture-absorbing and heat-generating fibers . Among all moisture-absorbing and heat-generating fibers, acrylate fibers have obvious advantages in terms of moisture absorption and water absorption, heat generation amount , service durability, etc., and are the most widely used in current moisture-absorbing and heat-generating products .

[0004] ​​​Currently, moisture-absorbing, heat-generating acrylate fibers are available on the market, such as Mizuno Corporation's Breath Thermo, Moisture Care from Toyobo Co., Ltd., and S from Toho Textile Co., Ltd. All unburners chemically modify polyacrylonitrile fibers and use amine reagents. Through the crosslinking and hydrolysis action of lucari, the nitrile groups in polyacrylonitrile fibers are converted. Converts to hydrophilic groups such as amide groups, carboxyl groups, and carboxyl group metal salts, thereby improving the moisture absorption of fibers. It significantly improves performance and can release a large amount of heat by absorbing moisture and water vapor. However, Currently, most moisture-absorbing, heat-generating acrylate fibers on the market are red in color, and There is a problem where the colors of products from different batches do not match, and the colors deepen over time. It is present and affects the stability of the product in use. In 2014, Mizuno Corporation announced that it had increased fluorescence. Using a whitening agent, Breath Thermo moisture-absorbing heat-generating acrylate fibers are modified, and the red color Although a product with reduced fluorescence and improved whiteness was obtained, the use of fluorescent agents does not affect the safety performance of the product in use. It also had a certain impact.

[0005] Therefore, how to further solve the color problem of moisture-absorbing, heat-generating acrylate fibers, different The challenge of expanding the application of this fiber in various application fields remains, particularly in the field of moisture-absorbing and heat-generating products. The issue of this fiber in the context of [the field] is a critical problem that urgently needs to be resolved. [Overview of the project] [Problems that the invention aims to solve]

[0006] However, currently, most moisture-absorbing, heat-generating acrylate fibers on the market are red in color. Furthermore, there is a problem where the colors of products from different batches do not match, and the colors deepen over time. It exists and affects the stability of the product's use, and currently the existing red color has decreased, and the white color Moisture-absorbing, heat-generating acrylate fiber products with improved color may have limitations in their use due to the use of fluorescent agents. It will have a certain impact on its safety performance.

[0007] This invention is based on chemical modification technology and utilizes polymer crosslinking and semi-crosslinking technology to enable multiple The hydrophilic functional groups of various types are semi-crosslinked on the surface of polyacrylonitrile fibers, and chemical reduction and acid After the chemical process, acrylate fibers with moisture-absorbing and heat-generating properties are obtained, and a multi-colored moisture-absorbing and heat-generating acrylate is produced. The objective is to provide a rate fiber and a method for manufacturing it. In this process, the manufacturing process By controlling the reaction time, reaction temperature, type of reagent, and material mixing ratio, different results can be achieved. Colored moisture-absorbing, heat-generating acrylate fibers can be obtained, and the colors can be white, cream, and beige. This invention includes colors such as red, yellow, orange, red, reddish-purple, and brown. The present invention, through an antioxidant fixing treatment, By controlling the generation of chromophores of different colored fibers, it is possible to achieve the effect of stabilizing the color of the fibers. The manufacturing method provides a method that significantly simplifies the manufacturing process and enables rapid industrialization. To facilitate production, and to significantly improve the hygroscopicity and color stability of the modified product, and to absorb After becoming damp, it can release more heat, making it more useful in areas such as winter insulation and heat generation from moisture absorption. It can be applied to various purposes. [Means for solving the problem]

[0008] 1. The white moisture-absorbing, heat-generating acrylate fiber described in the present invention is produced by a short-time two-bath molding method using polyacrylate By modifying lilonitrile fibers, white moisture-absorbing, heat-generating acrylate fibers are obtained, and the fibers absorb water molecules. A key feature is its ability to release a large amount of heat after collecting and adsorbing it.

[0009] To achieve the object of the above invention, the present invention provides the following technical solutions: The present invention provides a method for manufacturing white moisture-absorbing and heat-generating acrylate fibers, mixing a mixed solution of polyacrylonitrile fibers, a crosslinking agent and an antioxidant, and performing a chemical crosslinking reaction to obtain crosslinked modified polyacrylonitrile fibers, and mixing the crosslinked modified polyacrylonitrile fibers with a mixed solution of an alkali solution and an antioxidant to perform an alkali hydrolysis reaction to obtain hydrolytically modified moisture-absorbing and heat-generating acrylate fibers, including.

[0010] Preferably, in the polyacrylonitrile fibers, the color is white, the fineness is 1.2 to 15 D, and the length is 32 to 64 mm.

[0011] Preferably, the crosslinking agent in the crosslinking agent solution includes one or more of polyethylene, ethylenediamine, polyvinylamine, propanediamine, acrylic acid, polyacrylic acid, ethylene glycol or glycerin, and the concentration of the crosslinking agent in the crosslinking agent solution is 0.5 to 2.5 mol / L.

[0012] Preferably, the alkali solution is one or more of ammonia water, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution, and the concentration of the alkali solution is 2 to 4 mol / L.

[0013] Preferably, the antioxidant is calcium ascorbate,

[0014] and 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 h.

[0015] Preferably, the cross-linked polyacrylonitrile fibers are white in color.

[0016] Preferably, the temperature of the alkaline hydrolysis reaction is 125°C and the duration is 0.5 to 1 hour. .

[0017] Preferably, the hydrolysis-modified acrylate fiber is white in color.

[0018] 2. The cream-colored, beige, or yellow moisture-absorbing and heat-generating acrylate fiber described in the present invention is short Polyacrylonitrile fibers are modified using a two-bath molding method, resulting in cream, beige, or yellow colors. A colored, moisture-absorbing, heat-generating acrylate fiber is obtained, and after the fiber absorbs and adsorbs water molecules, a large amount of heat is released. It is characterized by its ability to release.

[0019] To achieve the objectives of the above invention, the present invention provides the following technical solutions: This invention provides a method for producing cream-colored, beige, or yellow moisture-absorbing, heat-generating acrylate fibers. death, A mixture of polyacrylonitrile fibers, a crosslinking agent, and an alkaline solution is mixed to perform chemical crosslinking. After the alkaline hydrolysis reaction is carried out, an antioxidant fixing treatment is performed, and the moisture-absorbing exothermic acrylate The step includes obtaining fibers, Preferably, the polyacrylonitrile fibers are white in color, have a fineness of 1.2 to 15D, and have a length The range is 32-64 mm.

[0020] Preferably, the crosslinking agent in the crosslinking agent solution is polyethylene, ethylenediamine, and poly Vinyl chloride, propanediamine, hydrated hydrazine, acrylic acid, polyacrylic acid , comprising one or more of ethylene glycol or glycerin, The concentration of the crosslinking agent in the aforementioned crosslinking agent solution is 0.5 to 2.5 mol / L.

[0021] Preferably, the alkaline solution is aqueous ammonia, sodium hydroxide solution, or potassium hydroxide. One or more of the following: solution, magnesium hydroxide solution, calcium hydroxide solution, The concentration of the aforementioned alkaline solution is 2-4 mol / L.

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

[0023] Preferably, the antioxidant fixing treatment is performed by treating the manufactured fibers with an antioxidant solution. be.

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

[0025] 3. The orange, red, reddish-purple, or brown moisture-absorbing and heat-generating acrylate fibers described in the present invention are effective for a long time. Polyacrylonitrile fibers are modified using a three-bath molding method, and then the fibers are subjected to an antioxidant fixing treatment. This process yields orange, red, reddish-purple, or brown moisture-absorbing, heat-generating acrylate fibers, and the fibers absorb water molecules. It is characterized by its ability to absorb and adsorb heat, and then release a large amount of heat.

[0026] To achieve the objectives of the above invention, the present invention provides the following technical solutions: This invention provides a method for producing orange, red, reddish-purple, or brown moisture-absorbing, heat-generating acrylate fiber modifications. death, A mixture of polyacrylonitrile fibers, a crosslinking agent, and an alkaline solution is mixed to perform chemical crosslinking. The steps include: carrying out a reaction and hydrolysis to obtain orange, moisture-absorbing, heat-generating acrylate fibers; The aforementioned orange moisture-absorbing, heat-generating acrylate fiber and oxidizing agent solution are mixed, and the fiber is subjected to an oxidation treatment. The process includes the step of obtaining red, reddish-purple, or brown moisture-absorbing, heat-generating acrylate fibers.

[0027] Preferably, the polyacrylonitrile fibers are white in color, have a fineness of 1.2 to 15D, and have a length The range is 32-64 mm.

[0028] Preferably, the crosslinking agent in the crosslinking agent solution is polyethylene, ethylenediamine, and poly Vinyl chloride, propanediamine, hydrated hydrazine, acrylic acid, polyacrylic acid , comprising one or more of ethylene glycol or glycerin, The concentration of the crosslinking agent in the aforementioned crosslinking agent solution is 0.5 to 2.5 mol / L.

[0029] Preferably, the alkaline solution is aqueous ammonia, sodium hydroxide solution, or potassium hydroxide. One or more of the following: solution, magnesium hydroxide solution, calcium hydroxide solution, The concentration of the aforementioned alkaline solution is 2-4 mol / L.

[0030] Preferably, the temperature for the chemical crosslinking and hydrolysis reaction is 115-125°C and the duration is 1-4 hours. be.

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

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

[0033] Preferably, the antioxidant fixing treatment is performed by treating the manufactured fibers with an antioxidant solution. be.

[0034] The antioxidant solution had a concentration of 1 mol / L, the solvent was water, the processing temperature was 65°C, and the processing time was 0.5 It is h. [Effects of the Invention]

[0035] This invention, based on chemical modification technology, modifies the basic structure of polyacrylonitrile fibers to various degrees. By changing the degree and using polymer crosslinking and semi-crosslinking technologies, multiple types of hydrophilic functionalities can be created. The base is semi-crosslinked onto the surface of polyacrylonitrile fibers, and after chemical reduction and oxidation processes, The present invention produces moisture-absorbing, heat-generating modified polyacrylonitrile fibers having multiple types of warm colors. The manufacturing method provided by strictly controls the process and technical conditions, thereby enabling the reaction Various chromophores such as imide groups, amide groups, carboxyl groups, and carboxylates are formed inside. This controls the content of color-forming agents and achieves the effect of very precisely controlling the color of the fibers, and is currently in the market Various problems arise with moisture-absorbing, heat-generating acrylate fibers depending on the fiber color, for example, multi-color The colors of the textile products do not match, and the colors change over time. The reagents used contain fluorescent agents. It can effectively solve various problems such as containing multiple types of fibers. It possesses various functions, including color, excellent super-moisture absorption, moisture absorption and heat generation, and deodorization, and is suitable for a wide range of application fields. It can be adapted to. [Brief explanation of the drawing]

[0036] [Figure 1] Schematic diagram of structural changes during the cross-linking reaction. [Figure 2] Schematic diagram of structural changes during the alkaline hydrolysis reaction. [Figure 3] The heat rise curve of multi-colored moisture-absorbing, heat-generating acrylate fibers. [Figure 4] Detection of the deodorizing performance of multi-colored moisture-absorbing, heat-generating acrylate fibers. [Modes for carrying out the invention]

[0037] This invention is based on the following concept and is studied. Unmodified acrylic fibers are white, After cross-linking modification and hydrolysis reaction, the fibers change to a cream, beige, or yellow color, and at time Over time, it gradually generates red in the air. The inventor, through related research, found that the fibers The color change is mainly due to the color development or auxiliary coloring functions of nitrogen and oxygen content generated during the modification of the fibers. This is caused by groups such as imide groups, amide groups, carboxyl groups, carboxylate salts, etc. We discovered that the formation of these functional groups absorbs ultraviolet or visible light through electronic transition effects. Furthermore, it causes a redshift phenomenon in the absorption peak in the ultraviolet-visible absorption spectrum (UV). As a result, the wavelength of the light absorption peak shifts towards longer wavelengths, and the light absorption wavelength gradually shifts from 435 nm. It gradually changes to 750nm, producing a color change that can be observed by the human eye. After studying the principles, the present invention efficiently and stably produces multi-colored moisture-absorbing, heat-generating acrylate fibers. The manufacturing method is provided, and the fibers come in multiple colors and have excellent properties such as super moisture absorption, moisture absorption and heat generation, and deodorization. It possesses multiple functions and can be well applied to spinning and weaving technologies, such as clothing and home textiles. This solves the troublesome problems caused by color issues in this field.

[0038] The multi-colored moisture-absorbing, heat-generating acrylate fibers described in the present invention will be explained in detail below.

[0039] The color change produced by the multi-colored moisture-absorbing, heat-generating acrylate fibers described in the present invention is primarily due to the principle of The reason is that, as different types and degrees of chemical reactions occur, imide groups are added to the fiber polymer chains. It generates chromophores or auxochromates such as amide groups, carboxyl groups, and carboxylates, and these functionalities Under the combined influence of the base, the light absorption peak wavelength of the fiber material gradually changes from 435 nm to 750 nm. It changes to m, and the color gradually changes from white to reddish. During fiber modification, an antioxidant is added. By using this method, the oxidative transformation of functional groups in fibers can be effectively suppressed, thereby preventing changes in the color of the fibers. Effectively suppresses the transformation.

[0040] The moisture-absorbing, heat-generating acrylate fiber described in the present invention undergoes the following structural changes during the crosslinking reaction: Under heating conditions, the addition of external energy affects the molecules inside the polyacrylonitrile fibers. The dense structure in which the chains are arranged can be disrupted, and at the same time, the addition of a crosslinking agent disrupts two adjacent molecular chains. The bridge structure can be connected, and the degree of swelling in the alkaline hydrolysis reaction can be reduced. The crosslinking agent generates a crosslinking reaction while simultaneously carrying out a certain degree of hydrolysis and oxidation. Furthermore, it reacts with nitrile groups on the fiber polymer chain to produce imide groups, amide groups, carboxyl groups, etc. It generates a color group or auxiliary color group, and further causes a redshift in the light absorption peak of the entire fiber. Depending on the degree of reaction, the wavelength of the light absorption peak is 350-480 nm, and at this stage the fibers The color of the material is cream, beige, or yellow.

[0041] The moisture-absorbing, heat-generating acrylate fiber described in the present invention undergoes the following structural changes during the hydrolysis reaction: The hydrolysis reaction that occurs in polyacrylonitrile fibers during this process is primarily This is a reaction between nitrile groups in fiber polymer chains and alkaline solutions, and in the usual case, the nitrile groups are It reacts with alkali at high temperatures, opening the carbon-nitrogen triple bond of the nitrile group, and reacts with alkali. First, an amide group is formed, and as the reaction proceeds sequentially, the amide group is replaced by a carboxyl group. It is hydrolyzed into carboxylate salts, and due to the extremely strong hydrophilic and swelling properties of both, fibers Some of it is broken down in an alkaline solution, and at the same time the fibers turn into a gel-like substance and become slippery. This affects normal use. However, after the crosslinking reaction, the crosslinks formed between adjacent polymer chains The resulting cross-linked structure can effectively increase the alkali-resistant stability of the fibers, and the resulting cross-linked modified polymer Acrylonitrile fibers undergo hydrolysis reactions with alkali, but only a very small portion of them undergo the reaction. The mido group is oxidized to the carbon-oxygen double bond, and the nitrates in many parts where no other cross-linking reaction occurred A lyl group is present, and in this process, it reacts with alkali to form an amide group, a carboxyl group, or a carboxyl group. It generates rubonate salts. At the same time, it generates carbon nitrogen such as amide groups, carboxyl groups, or carboxylate salts. As a chromophore containing double bonds is formed, a redshift occurs in the light absorption peak of the fiber, and the length of the chromophore is longer. It continues to move in the wavelength direction, 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 described in the present invention undergoes the following structural changes during the oxidation reaction: Polyacrylonitrile fibers are converted into acrylate fibers after crosslinking and hydrolysis modification. The nitrile group, which is the fundamental characteristic group of fibers, is an amino group, amide group, carboxyl group, or carboxyl group. It is converted to a base such as rubonate, and at the same time, the color of the fiber changes from its original white to orange or red. Furthermore, the color of the fibers continues to change towards red over time, and this is because the fibers undergo a cross-linking reaction. In polymer chains, many imide groups remain after the carbon-nitrogen triple bond of the nitrile group is broken. Furthermore, the imide group is converted to a carbon-oxygen double bond under the effect of prolonged air oxidation, resulting in light absorption. By changing the wavelength of the light and shifting towards longer wavelengths, the red color of the fiber becomes more prominent. That is the case.

[0043] This invention provides a method for producing multi-colored moisture-absorbing, heat-generating acrylate fibers. Polyacrylonitrile fibers are mixed with a crosslinking agent or a mixed solution of a crosslinking agent and an antioxidant, and chemically... The process includes the step of performing a crosslinking reaction to obtain crosslinked polyacrylonitrile fibers. The acrylonitrile fibers are white in color, preferably 1.2 to 15D in fineness, and preferably in length. The diameter is 38-56 mm. In the present invention, the concentration of the crosslinking agent in the crosslinking agent solution is preferred. Or 0.5 to 2.5 mol / L, more preferably 0.8 to 1.5 mol / L, most preferably Or it is 0.9 to 1.1 mol / L. In the present invention, crosslinking in the crosslinking agent solution The agents are preferably polyethylene, ethylenediamine, polyvinyl chloride amine, and propane. Diamine, hydrated hydrazine, acrylic acid, polyacrylic acid, ethylene glycol or glycerin The crosslinking agent comprises one or more types of serine, and the crosslinking agent is two or more of the specific selections above. In the above case, the present invention does not impose any special limitations on the blending ratio of the specific substances mentioned above. The mixture can be mixed in any desired ratio. In the present invention, the solvent in the crosslinking agent solution is Preferably, the solvent is water and / or ethanol, and if the solvent is water and ethanol, The invention does not impose any special limitations on the ratio of water and ethanol used, and any It is sufficient to mix them according to the mixing ratio. In the present invention, the polyacrylonitrile fiber and the crosslinking agent solution The mass ratio of the crosslinking agent in the liquid is preferably (7-1):(1-3), more preferably (4. 5~1):(1~1.5), most preferably (2~1):1. In the present invention, The temperature of the chemical crosslinking reaction is preferably 115-125°C, more preferably 117-123°C. The temperature is most preferably 119-121°C, and the time is preferably 0.5-2 hours. Furthermore, the antioxidant is calcium ascorbate, and its concentration in the mixed solution is 1 The concentration is mol / L. The present invention does not impose any special limitations on the aforementioned mixing process. You can use a process that is well known to those skilled in the art.

[0044] The cross-linked polyacrylonitrile fiber, an alkaline solution or an alkaline solution and an antioxidant The mixed solution is mixed, and an alkaline hydrolysis reaction is carried out to obtain hydrolysis-modified acrylate fibers. To obtain. In the present invention, the alkaline solution is preferably aqueous ammonia and sodium hydroxide. One of the following: solution, potassium hydroxide solution, magnesium hydroxide solution, calcium hydroxide solution It consists of one or more species, and the concentration of the alkaline solution is preferably 2-4 mol / L, more preferably More preferably, it is 2.5 to 3.5 mol / L, and most preferably 2.8 to 3.2 mol / L. In the invention, the cross-linked modified polyacrylonitrile fiber and the alkali in the alkaline solution The mass ratio is preferably (3-1):(1-2), more preferably (1.5-1):(1- 1.5) Most preferably (1.2~1):1. In the present invention, the alkalinity The temperature of the hydrolysis reaction is preferably 125°C, and the duration is preferably 1.5 to 4 hours. Preferably 1.6 to 1.9 hours, most preferably 1.7 to 1.8 hours. The antioxidant is calcium ascorbate, and its concentration in the mixed solution is 1 mg. The ratio is l / L. In the present invention, the color of the hydrolysis-modified acrylate fiber is preferably white. The color is cream, beige, or yellow. The present invention relates to the aforementioned mixing process. There are no particular limitations; any process well known to those skilled in the art may be used.

[0045] The modified hydrolyzed acrylate fiber and the oxidizing agent solution are mixed and an oxidation reaction is carried out. A moisture-absorbing, heat-generating acrylate fiber is obtained. 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, most preferably 5 to It is 8 mol / L. 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 The oxidizing agent is one or more of the above specific selections, and the oxidizing agent is two or more of the above specific selections. In addition, the present invention does not have any special limitations on the blending ratio of the above-mentioned specific substances, and any It is sufficient to mix them according to the mixing ratio. In the present invention, the modified hydrolysis-modified acrylate fiber and The mass ratio of the oxidizing agent in the oxidizing agent solution is preferably (3-1):(1-11), more preferably The ratio is 1:(1~10), most preferably 1:(2~4). The present invention relates to the aforementioned mixed product With respect to Seth, there are no special limitations and processes that are well known to those skilled in the art. It can be used as is. In the present invention, the temperature of the oxidation reaction is preferably 85 to 125°C. Preferably 95-115°C, most preferably 100-110°C, and the time is preferably The incubation period is 1 to 1.5 hours, more preferably 1 to 1.2 hours. After the oxidation reaction is completed, the main The invention also preferably includes washing and drying in sequence, and the present invention relates to the washing and drying process There are no special limitations on the process, and the process is well known to those skilled in the art. It can be used as is. The color of the oxidized, moisture-absorbing, heat-generating acrylate fiber is orange, red, reddish-purple, or brown. It is a color.

[0046] The multicolored moisture-absorbing, heat-generating acrylate fibers described in the present invention are obtained through the above-mentioned multiple complex chemical modification processes. Manufactured by [unclear], the modified fibers have excellent moisture absorption and water absorption properties, suitable for temperatures of 20°C and 65% RH. Under environmental conditions, it can achieve a moisture absorption and water absorption performance of 21-42%. Furthermore, the present invention is described below. Multicolored moisture-absorbing and heat-generating acrylate fibers can exhibit a noticeable moisture-absorbing and heat-generating effect within 10 seconds. The maximum temperature after moist heating can reach 42.2°C.

[0047] The multicolored moisture-absorbing, heat-generating acrylate fibers described in the present invention are obtained through the above-mentioned multiple complex chemical modification processes. Manufactured using a special process, the modified fiber surface has many pore structures, effectively eliminating unpleasant odors and malodors from the air. It can be adsorbed to a specific target, and the material of the modified fiber can react to acids and alkalis to a certain extent simultaneously. Therefore, it has excellent deodorizing and odor-eliminating properties.

[0048] The multi-colored moisture-absorbing, heat-generating acrylate fibers described in the present invention may be used alone or in combination with other types. Used simultaneously with fiber raw materials, such as natural fibers, organic fibers, artificial fibers, regenerated fibers, and inorganic fibers. It is possible to use moisture-absorbing, heat-generating acrylate fibers in different color palettes depending on different needs and applications. By selecting this option, you can use different raw material blending ratios.

[0049] For example, the multicolor moisture-absorbing and heat-generating acrylate fibers described in this invention include cotton, linen, silk, wool, and rayon. It can be blended with fibers such as cellulose, Tencel, cupro, polyester, or nylon to produce yarn. Here, the moisture-absorbing, heat-generating acrylate fiber content is 5-90%, including cotton, linen, silk, wool, rayon, and twill. The fiber content of materials such as cellulose, cupro, polyester, and nylon is 10-95%, as described above. Yarns manufactured from multi-colored moisture-absorbing, heat-generating acrylate fibers are produced using vortex spinning and ring spinning. It can be manufactured using conventional spinning methods such as spinning, silo spinning, or compact silo spinning. The yarn is a composite yarn of multiple types of fibers in parallel, and the yarn has a multi-colored moisture-absorbing and heat-generating element. The acrylate fiber content is 10% or more, meaning it has a remarkable moisture-absorbing and heat-generating effect and deodorizing effect. It can produce a deodorizing effect, with a maximum heating temperature of 8.8℃ and a deodorizing effect of 98%. The multi-colored moisture-absorbing, heat-generating acrylate fiber described in the present invention is characterized by the above, and is made of cotton, linen, etc. , and blends of fibers such as silk, wool, rayon, Tencel, cupro, polyester, or nylon. After processes such as blending, carving, wrapping, and setting, hollow cotton flocks are manufactured, and here The moisture-absorbing, heat-generating acrylate fiber content ranges from 5% to 90%, and the materials include cotton, linen, silk, wool, rayon, and Tencel. The fiber content of cupro, polyester, or nylon is 10-95%, and the multicolor Hollow cotton flocks made from moisture-absorbing, heat-generating acrylate fibers are used in polyester wadding. Made from adhesive-free cotton, PrimaLoft, needle-punched cotton, or spunlace cotton, etc. The hollow cotton floc is a composite type hollow cotton floc in which multiple types of fibers are uniformly mixed. The hollow cotton flock contains 10% and 10% of moisture-absorbing, heat-generating acrylate fibers. It is superior, meaning it can have a remarkable moisture-absorbing and heat-generating effect and a deodorizing effect, and the maximum heat generation temperature It can reach a temperature of 2.4℃ and is characterized by a deodorizing effect of 97% or more.

[0050] The multi-colored moisture-absorbing, heat-generating acrylate fiber product described in the present invention can be applied to clothing products. For example: underwear, undergarments, shirts, T-shirts, jackets, sweaters, pants, jackets Windbreaker, padded jacket, jacket, hat, earmuffs, scarf, gloves, socks, shoulder pads And, supporters, arm warmers, leg warmers, belly warmer, elbow pads, mask, tie It is Tsu.

[0051] The multi-colored moisture-absorbing, heat-generating acrylate fiber product described in the present invention is suitable for home textile products. It can be used for various purposes, such as: futons, comforters, mattresses, pillows, mattress pads, pillow pads, etc. Covers, fitted sheets, pillowcases, multi-purpose covers, cushions, carpets, rugs, sofas - Covers, kotatsu, blankets, pet beds, slippers, room shoes, sleeping bags, wool These include cloth, fitted blankets, throw blankets, and towel blankets.

[0052] Example 1 20g of polyacrylonitrile fiber (white in color, fineness 1.2D, length 38mm) , 200 mL mixed solution of ethylenediamine and calcium ascorbate (solvent is water, ethylenediamine The concentration of ethylenediamine is 0.5 mol / L, and the concentration of calcium ascorbate is 1 mol It is added to ( / L) and a chemical crosslinking reaction is carried out (the temperature of the chemical crosslinking reaction is 115°C and the time is 1 hour). Next, we obtain cross-linked modified polyacrylonitrile fibers, 20 g of the cross-linked modified polyacrylonitrile fiber is mixed with 200 mL of a 2 mol / L solution. A mixed solution of ammonia water and 1 mol / L calcium ascorbate (solvent is water, ammonia (Add to a solution with a water concentration of 2 mol / L and calcium ascorbate concentration of 1 mol / L) An alkaline hydrolysis reaction (temperature 115°C, time 1 hour) is carried out, producing a white, hygroscopic, exothermic ammonium compound. Relate fibers (white in color, with a moisture content of 21.4%, and after absorbing moisture, the fibers exhibit significant heat energy) (It was possible to release moisture, and the temperature after moisture absorption and heat generation 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 mixed solution of ethylenediamine and aqueous ammonia (solvent is water, ethylenediamine The solution is added to a solution with a concentration of 1 mol / L (ammonia solution with a concentration of 2 mol / L), and chemical crosslinking is performed. 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 manufacturing process is carried out. The fibers are then treated with an antioxidant solution (solvent is water, antioxidant is calcium ascorbate, concentrated The solution is added to a solution of 1 mol / L and subjected to an antioxidant fixation treatment (treatment temperature 65°C, time 0.5°C). h) Moisture-absorbing, heat-generating acrylate fiber (color: cream, moisture content reaches 23.2%), moisture absorption The fibers, after being soaked in water, were able to release a significant amount of heat, and the temperature after moisture absorption and heat generation reached a maximum of 35.7°C. I got it.

[0054] Example 3 20g of polyacrylonitrile fiber (white in color, 3.3D fineness, 51mm in length) , 200 mL mixed solution of ethylenediamine and aqueous ammonia (solvent is water, ethylenediamine The solution is added to a solution with a concentration of 2 mol / L (ammonia solution with a concentration of 2 mol / L), and chemical crosslinking is performed. 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 manufactured fibers are treated with an antioxidant solution (solvent is water, antioxidant is calcium ascorbate). (Added to a solution of 1 mol / L) and subjected to antioxidant fixation treatment (treatment temperature 65°C, time 0 (0.5h) was performed, and the moisture-absorbing, heat-generating acrylate fiber (yellow in color, with a moisture content of 23.8%) absorbed. The fibers, after absorbing moisture, were able to release a significant amount of heat, reaching a maximum temperature of 35.9°C after heat generation. ) was obtained.

[0055] Example 4 20g of polyacrylonitrile fiber (white in color, 5.5D fineness, 64mm in length) , 200 mL mixed solution of hydrated hydrazine and aqueous ammonia (solvent is water, hydrated hydrazine The solution is added to a 1 mol / L concentration of ammonia water (4 mol / L concentration) and chemical crosslinking and aluminum A potassium hydrolysis reaction is carried out (the temperature of the chemical reaction is 120°C, and the time is 2 hours), and then the fibers are processed. 200 mL of ammonium persulfate solution (solvent is water, concentration of ammonium persulfate is 0.5%) Add to (mol / L) and carry out the oxidation reaction (the temperature of the oxidation reaction is 115°C and the time is 1 hour). Next, the manufactured fibers are treated with an antioxidant solution (solvent is water, antioxidant is calcium ascorbate). Cium (at a concentration of 1 mol / L) was added, and an antioxidant fixation treatment was performed (treatment temperature 65°C, hour The process involves a 0.5-hour interval, and the moisture-absorbing, heat-generating acrylate fiber (orange in color, with a moisture content of 24.3%) is used. Furthermore, the fibers, after absorbing moisture, can release a significant amount of heat, reaching a maximum temperature of 37.8°C after heat generation. (Achieved)

[0056] Example 5 20g of polyacrylonitrile fiber (white in color, 5.5D fineness, 64mm in length) , 200 mL mixed solution of hydrated hydrazine and sodium hydroxide (solvent is water, hydrated hydrazine The solution was added to a 1.5 mol / L concentration (with a sodium hydroxide concentration of 2 mol / L) and then chemically crosslinked. Then, an alkaline hydrolysis reaction is carried out (the temperature of the chemical reaction is 125°C, and the time is 2 hours), and then The fibers are treated with 200 mL of potassium permanganate solution (solvent is water, concentration of potassium permanganate). The solution is added to 2 mol / L and an oxidation reaction is carried out (the temperature of the oxidation reaction is 115°C, and the time is 1h) Next, the manufactured fibers are treated with an antioxidant solution (solvent is water, antioxidant is ascorbyl). Calcium phosphate (concentration 1 mol / L) is added, and an antioxidant fixation treatment is performed (treatment temperature 65°C). The process involves a temperature of ℃, a time of 0.5 hours, and the use of moisture-absorbing, heat-generating acrylate fiber (red in color, with a moisture content of 25%). Reaching 9%, the fibers, after absorbing moisture, can release a significant amount of heat, with temperatures reaching a maximum of 38°C after heat generation. The temperature reached 0.7℃.

[0057] Example 6 20g of polyacrylonitrile fiber (white in color, 7D fineness, 64mm in length), 2 00 mL mixed solution of hydrated hydrazine and sodium hydrate (solvent is water, concentration of hydrated hydrazine) It is added to a solution of 2 mol / L (sodium hydroxide concentration of 3 mol / L), and chemical crosslinking and aluminum are performed. A potassium hydrolysis reaction is carried out (the temperature of the chemical reaction is 125°C, and the time is 3 hours), and then the fibers are processed. 200 mL of potassium permanganate solution (solvent is water, concentration of potassium permanganate is 4 mg) Add to (ol / L) and carry out the oxidation reaction (the temperature of the oxidation reaction is 125°C and the time is 1.5h). Next, the manufactured fibers are treated with an antioxidant solution (solvent is water, antioxidant is ascorbic acid). Calcium (at a concentration of 1 mol / L) was added, and an antioxidant fixation treatment was performed (treatment temperature: 65°C). (Time: 0.5h), Moisture-absorbing, heat-generating acrylate fiber (color: reddish-purple, moisture content reaches 28.4%) After absorbing moisture, the fibers can release a significant amount of heat, reaching a maximum temperature of 39.6°C. (I obtained)

[0058] Example 7 20g of polyacrylonitrile fiber (white in color, 15D fineness, 64mm in length), 200 mL mixed solution of hydrated hydrazine and sodium hydroxide (solvent is water, concentration of hydrated hydrazine) The solution is 2.5 mol / L, and the sodium hydroxide concentration is 4 mol / L. Chemical crosslinking and Then, an alkaline hydrolysis reaction is carried out (the temperature of the chemical reaction is 125°C, and the time is 4 hours), and then the fibers are processed. The fiber is added to 200 mL of sulfuric acid solution (solvent is water, sulfuric acid solution concentration is 11.5 mol / L). Then, an oxidation reaction is carried out (the temperature of the oxidation reaction is 125°C, and the time is 1.5 hours), and then the product is manufactured. The fibers are treated with an antioxidant solution (solvent is water, antioxidant is calcium ascorbate, concentration is...) It was added to 1 mol / L and subjected to antioxidant fixation treatment (treatment temperature 65°C, time 0.5h). , moisture-absorbing heat-generating acrylate fiber (color: brown, moisture content reaches 42%, and the fiber after moisture absorption is, A significant amount of heat was released, and the temperature after moisture absorption and heat generation reached a maximum of 44.2°C.

[0059] The foregoing describes only preferred embodiments of the present invention, and those skilled in the art will see no departure from the principles of the present invention. Multiple improvements and enhancements can be made without any need to protect the present invention, and these improvements and enhancements are also protected by the present invention. It should belong to the range.

Claims

1. Moisture-absorbing, heat-generating acrylics containing white, cream, beige, yellow, orange, red, reddish-purple, or brown. A method for producing ribe fibers, Using polyacrylonitrile fibers as raw materials, cross-linking reaction, alkaline hydrolysis reaction, oxidation reaction and After the antioxidant fixing treatment, there are different colors. In the aforementioned crosslinking reaction, polyacrylonitrile fibers are reacted with a crosslinking agent to modify the polyacrylonitrile fibers. The objective is to obtain lilonitrile fibers, and the crosslinking agent is ethylene, ethylenediamine, and poly Vinyl chloride, propanediamine, hydrated hydrazine, acrylic acid, polyacrylic acid , ethylene glycol, or glycerin, one or more of these, The aforementioned alkaline hydrolysis reaction involves reacting modified polyacrylonitrile fibers with an alkaline solution. The objective is to obtain hydrolyzed acrylate fibers, and the alkaline solution is ammonia Water, sodium hydroxide solution, potassium hydroxide solution, magnesium hydroxide solution, or potassium hydroxide One or more types of calcium solutions The aforementioned oxidation reaction involves oxidizing hydrolyzed acrylate fibers with an oxidizing agent, resulting in a multicolor absorption reaction. The objective is to obtain a moist heat-generating acrylate fiber, wherein the oxidizing agent is concentrated sulfuric acid, nitric acid, or ammonium persulfate. It is one or more of the following: nium, potassium permanganate, or sodium hypochlorite. 、 The aforementioned antioxidant fixing treatment involves applying an antioxidant treatment to the fibers to prevent oxidation, thereby reducing nitrogen within the fibers. The purpose is to prevent discoloration of the fibers by further oxidative conversion of the element-containing groups, and the oxidation The inhibitor is calcium ascorbate. The polyacrylonitrile fibers are white in color, have a fineness of 1.2 to 15D, and a length of 38 to 56. mm The concentration of the crosslinking agent in the crosslinking agent solution is 0.9 to 1.1 mol / L. The mass ratio of the polyacrylonitrile fiber to the crosslinking agent in the crosslinking agent solution is (2-1): It is 1, The temperature of the crosslinking reaction was 119-121°C, and the duration was 0.5-2 hours. The concentration of the alkaline solution is 2.8 to 3.2 mol / L. The mass ratio of the cross-linked polyacrylonitrile fiber to the alkali in the alkaline solution is (1 . 2-1): 1, The temperature of the alkaline hydrolysis reaction was 125°C, and the duration was 1.7 to 1.8 hours. The concentration of the oxidizing agent solution is 5-8 mol / L. The mass ratio of the modified hydrolyzed acrylate fiber to the oxidizing agent in the oxidizing agent solution is 1: (2-4) The temperature of the oxidation reaction is 100 to 110°C, and the duration is 1 to 1.2 hours. Moisture-absorbing, heat-generating acrylics containing white, cream, beige, yellow, orange, red, reddish-purple, or brown. A method for manufacturing relative fibers.

2. The aforementioned moisture-absorbing material includes white, cream, beige, yellow, orange, red, reddish-purple, or brown. The colors of the heat-activated acrylate fibers are white, cream, beige, yellow, orange, red, and reddish-purple. The manufacturing method according to claim 1, characterized in that it is one of the brown varieties.

3. The aforementioned moisture-absorbing material includes white, cream, beige, yellow, orange, red, reddish-purple, or brown. The color change of thermoacrylate fibers is due to the imide groups, amide groups, and calcium contained within the fibers. This is caused by a boxyl group, a carboxylate chromophore or auxochromophore, and is provided by the present invention. The method described in claim 1 is characterized by its ability to precisely control and fix the color of the fibers. Construction method.

4. The aforementioned moisture-absorbing material includes white, cream, beige, yellow, orange, red, reddish-purple, or brown. Thermoacrylate fibers offer multi-functional properties including excellent moisture absorption, moisture-absorbing and heat-generating capabilities, and deodorizing properties. The manufacturing method according to claim 1, characterized by having

5. The aforementioned moisture-absorbing material includes white, cream, beige, yellow, orange, red, reddish-purple, or brown. Thermoacrylate fibers are characterized by their ability to be applied to different situations depending on their color and specifications. The manufacturing method described in item 3.

6. The aforementioned moisture-absorbing material includes white, cream, beige, yellow, orange, red, reddish-purple, or brown. Thermoacrylate fibers are used in various types of yarn weaving, knitting, weaving, nonwoven fabrics, and hollow fiber flocking. It can be applied to manufacturing, and the aforementioned fiber structure can be applied to clothing products, bedding products, and furniture products. The manufacturing method according to claim 4, characterized by the following.

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