CN109689951B - Modacrylic fiber, method for producing the fiber, and fiber structure containing the fiber - Google Patents
Modacrylic fiber, method for producing the fiber, and fiber structure containing the fiber Download PDFInfo
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- CN109689951B CN109689951B CN201680089157.3A CN201680089157A CN109689951B CN 109689951 B CN109689951 B CN 109689951B CN 201680089157 A CN201680089157 A CN 201680089157A CN 109689951 B CN109689951 B CN 109689951B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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Abstract
An object of the present invention is to provide: a modacrylic fiber which can be produced by a simpler process than the conventional one. The object is achieved by a modified acrylic fiber having a carboxyl group of 0.2 to 4.0mmol/g, a solubility in a 58% aqueous solution of sodium thiocyanate of 95% or more, and a solubility in dimethylformamide of 50% or less.
Description
Technical Field
The present invention relates to a modacrylic fiber, a method for producing the fiber, and a fiber structure containing the fiber.
Background
In recent years, because of the growing awareness of comfort, development of a material having a moisture-absorbing function has been required, and development in the field of fibers has been actively conducted. For example, known are: crosslinked acrylate fibers obtained by chemically modifying acrylic fibers (patent document 1). The fiber contains a crosslinked structure and a carboxyl group, and is a fiber having excellent moisture absorption properties.
However, in the production of such fibers, a step of introducing a crosslinked structure with hydrazine and a step of hydrolyzing for introducing a carboxyl group are required, and further, a step of removing the residue of the chemical used in the reaction is required after each step. In addition, these steps require a high temperature and a long time. Therefore, it is difficult to produce the fiber by a continuous process, and the production must be performed by a batch process with low productivity.
In addition, in the case of acrylic fibers having a carboxyl group, there are known: an acrylic fiber comprising an acrylonitrile polymer containing a monomer having a carboxyl group such as acrylic acid as a copolymerization component. However, if a large amount of acrylic acid is copolymerized, spinning becomes difficult, and thus it is difficult to exhibit high hygroscopicity. In addition, in the case of the use for clothing, there is a problem that the dye is easily eluted under alkaline conditions such as alkaline soaping during dyeing.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-132858
Disclosure of Invention
Problems to be solved by the invention
As described above, conventionally, there has been known a fiber in which moisture absorption is imparted to an acrylic fiber, but the production process is extensive, the productivity is low, or it is difficult to improve moisture absorption. The present invention has been made in view of the above-described current state of the art, and an object thereof is to provide: a hygroscopic acrylic fiber which can be produced by a simpler process than the conventional ones.
Means for solving the problems
The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: the present inventors have completed the present invention by obtaining a modified acrylic fiber while maintaining practical fiber properties without crosslinking treatment by spinning a spinning dope containing an acrylic polymer dissolved therein from a nozzle, subjecting the spun dope to coagulation, washing with water, and drawing to obtain an undried fiber, and hydrolyzing the obtained undried fiber.
That is, the present invention is achieved by the following means.
(1) A modified acrylic fiber characterized by having 0.2 to 4mmol/g of carboxyl groups, having a solubility in a 58% aqueous solution of sodium thiocyanate of 95% or more and a solubility in dimethylformamide of 50% or less.
(2) A modified acrylic fiber characterized by having 0.2 to 4mmol/g of carboxyl groups, having a solubility in a 58% aqueous sodium thiocyanate solution of 95% or more and a solubility in a 1g/L aqueous sodium carbonate solution of 5% or less.
(3) The modified acrylic fiber according to the item (1) or (2), characterized in that the saturated moisture absorption at 20 ℃ X65% RH is 3% or more.
(4) The modacrylic fiber according to any one of (1) to (3), wherein the carboxyl group is present throughout the entire fiber.
(5) A process for producing a modified acrylic fiber, characterized by comprising spinning a spinning dope containing an acrylic polymer dissolved therein from a nozzle, subjecting the spinning dope to coagulation, washing with water and drawing to obtain an undried fiber, and hydrolyzing the undried fiber.
(6) The process for producing a modacrylic fiber according to (5), wherein the moisture content of the undried fiber is 20 to 250%.
(7) A fiber structure comprising the modacrylic fiber described in any one of (1) to (4).
ADVANTAGEOUS EFFECTS OF INVENTION
The present inventors have found that, by spinning a spinning dope containing an acrylonitrile polymer dissolved therein from a nozzle, subjecting the spinning dope to coagulation, washing with water, and drawing to obtain undried fibers, and hydrolyzing the obtained undried fibers, it is possible to obtain acrylonitrile fibers having moisture absorption properties while maintaining practical fiber properties without crosslinking treatment. The fiber can be continuously produced by a common fiber production facility according to the above production method, and the productivity is high. The fiber exhibits not only moisture absorption but also properties such as deodorization, flame retardancy, antibacterial properties, antiviral properties, and antiallergic properties as described later, and thus can be used in various products and applications.
Detailed Description
The modified acrylic fiber of the present invention can be obtained as follows: the spinning dope containing the acrylonitrile polymer dissolved therein is spun from a nozzle, and then subjected to coagulation, washing with water, and drawing to obtain undried fibers, and the obtained undried fibers are hydrolyzed to obtain the acrylic fiber. The method for obtaining the modacrylic fiber of the present invention is described in detail below.
First, the acrylonitrile polymer as a raw material contains acrylonitrile as a polymerization composition in an amount of preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 85% by weight or more. Therefore, as the acrylonitrile polymer, in addition to acrylonitrile homopolymer, a copolymer of acrylonitrile and another monomer can be used. The other monomer in the copolymer is not particularly limited, and examples thereof include vinyl halides and vinylidene halides; (meth) acrylate (note that the expression (meth) indicates both a user who has the methyl group attached and a user who has not attached the methyl group); sulfonic acid group-containing monomers such as methallylsulfonic acid and p-styrenesulfonic acid, and salts thereof, acrylamide, styrene, and vinyl acetate.
Next, the case where the above-mentioned acrylonitrile-based polymer is fiberized by wet spinning and an inorganic salt such as sodium rhodamine is used as a solvent will be described below. First, the above-mentioned acrylonitrile polymer is dissolved in a solvent to prepare a spinning dope. The spinning dope is spun from a nozzle, and then subjected to coagulation, washing with water, and drawing steps, whereby the moisture content of the undried fiber after drawing (hereinafter also referred to as gel-like acrylic fiber) is 20 to 250 wt%, preferably 25 to 130 wt%, and more preferably 30 to 100 wt%.
Here, when the water content of the gel-like acrylic fiber is less than 20% by weight, the agent in the hydrolysis treatment described later may not penetrate into the fiber, and carboxyl groups may not be formed in the entire fiber. When the amount exceeds 250% by weight, the fiber contains a large amount of water therein, and the fiber strength becomes too low, so that the spinnability is undesirably reduced. When the fiber strength is regarded as high, it is desirable that the fiber strength is in the range of 25 to 130 wt%. Further, there are various methods for controlling the water content of the gel-like acrylic fiber within the above range, and for example, the coagulation bath temperature is desirably from-3 ℃ to 15 ℃, preferably from-3 ℃ to 10 ℃, and the draw ratio is desirably from 5 to 20, preferably from 7 to 15.
The gel-like acrylic fiber is then subjected to hydrolysis treatment. By this treatment, nitrile groups in the gel-like acrylic fiber are hydrolyzed to generate carboxyl groups.
Examples of the hydrolysis treatment include the following: the heat treatment is performed in a state of being impregnated or impregnated with an alkaline aqueous solution such as an alkali metal hydroxide, an alkali metal carbonate, or ammonia, or an aqueous solution such as nitric acid, sulfuric acid, or hydrochloric acid. Specific treatment conditions include the range of the amount of the carboxyl group, and the concentration of the treatment agent, the reaction temperature, the reaction time, and the like are suitably set, and in general, it is preferable to industrially and industrially impregnate 0.5 to 20% by weight, preferably 1.0 to 15% by weight of the treatment agent into the fiber and draw the fiber, and then treat the fiber at 100 to 140 ℃, preferably 110 to 135 ℃ for 10 to 60 minutes in a hot and humid atmosphere. The hot and humid atmosphere is an atmosphere filled with saturated steam or superheated steam.
In the fibers subjected to the hydrolysis treatment as described above, salt-type carboxyl groups are generated in which cations such as alkali metal, ammonium and the like according to the kind of alkali metal hydroxide, alkali metal carbonate, ammonia and the like used in the hydrolysis treatment are counter ions, and then, if necessary, a treatment for converting the counter ions of the carboxyl groups may be performed. The carboxyl group may be formed in a salt form by ion exchange treatment with an aqueous solution of a metal salt such as nitrate, sulfate, or hydrochloride, and the desired metal ion may be used as a counter ion. Further, by adjusting the pH of the aqueous solution, the concentration and type of the metal salt, counter ions of different types may be mixed and present, or the ratio thereof may be adjusted.
As described above, the modacrylic fibers of the present invention can be obtained and, if necessary, washed with water and dried. Although the case of using an inorganic salt such as sodium rhodamine or the like as the solvent has been described above, the same conditions apply to the case of using an organic solvent. However, since the type of the solvent is different, the temperature suitable for the solvent is selected for the coagulation bath temperature, and the water content of the gel-like acrylic fiber is controlled to be within the above range.
The modacrylic fibers of the present invention obtained as described above have a combination of properties that has not been possible so far. Namely, the following features are provided: has a carboxyl group content of 0.2 to 4.0mmol/g, has a solubility in a 58% aqueous solution of sodium thiocyanate of 95% or more, and has a solubility in dimethylformamide of 50% or less, or has a solubility in a 1g/L aqueous solution of sodium carbonate of 5% or less.
From the above-mentioned characteristics of the modacrylic fiber of the present invention, it is presumed that the structure of the fiber is not as follows. That is, it is considered that the acrylic polymer constituting the fiber has no intermolecular crosslinked structure due to covalent bonds, because of the property that the solubility in a 58% sodium thiocyanate aqueous solution, which is a good solvent for the acrylic polymer, is 95% or more.
On the other hand, similarly, it is considered that the increase in hydrophilicity by hydrolyzing the introduced carboxyl group affects the property that the solubility of dimethylformamide, which is a good solvent for the acrylonitrile-based polymer, is 50% or less. However, in the case of copolymerizing a monomer containing a carboxyl group such as methacrylic acid in an acrylonitrile polymer, since it is soluble in dimethylformamide, it is not easy to consider that the above-mentioned characteristics are derived from the presence of a carboxyl group alone. In the production process of the present invention, since the gel-like acrylic fiber is subjected to hydrolysis treatment, it is considered that the chemical agent penetrates deep into the fiber and hydrolyzes throughout the entire fiber, rather than sequentially hydrolyzing from the fiber surface. In addition, when viewed microscopically, an acrylic fiber generally contains a mixture of oriented crystalline portions of the acrylonitrile polymer and structurally disordered amorphous portions. It is therefore considered that the crystalline portion is hydrolyzed from the outside thereof, but the amorphous portion is hydrolyzed as a whole. As a result, it is considered that, microscopically, a part of the crystal portion remains as a portion having a high nitrile group concentration without undergoing hydrolysis, and the amorphous portion becomes a portion having a high carboxyl group concentration. In addition, since the portion having a high carboxyl group concentration has particularly high hydrophilicity, it is presumed that the solubility in dimethylformamide is lowered.
The characteristic that the solubility in a 1g/L aqueous solution of sodium carbonate is 5% or less indicates that the polymer constituting the fiber of the present invention has a carboxyl group and is not easily eluted in an alkaline aqueous solution. In the fiber of the present invention, as described above, it is considered that the portion having a high nitrile group concentration exists over the entire fiber, and the portion having a high nitrile group concentration has alkali resistance, and therefore, it is estimated that the solubility in a 1g/L sodium carbonate aqueous solution is reduced.
From the above, it is presumed that: the structure of the modacrylic fiber of the present invention is a structure in which a portion having a high carboxyl group concentration and a portion having a high nitrile group concentration are present throughout the entire fiber, without having an intermolecular crosslinked structure due to covalent bonds.
As is clear from the above, in the present invention, a fiber having the above-described characteristics can be obtained by subjecting a gel-like acrylic fiber to hydrolysis treatment. When the hydrolysis treatment is performed on the acrylic fiber after drying without using the gel-like acrylic fiber, that is, the undried fiber after drawing, the chemical does not penetrate deep into the fiber and is sequentially hydrolyzed from the fiber surface, and therefore, a structure in which the number of carboxyl groups is large in the surface layer portion of the fiber and small in the deep inside of the fiber is derived. The fibers having such a structure cause elution of water or the like in the surface layer portion of the fibers, and are not practically durable.
In addition, the property that the solubility in a 58% aqueous solution of sodium thiocyanate is 95% or more in the modacrylic fiber of the present invention indicates the possibility of reuse due to dissolution that has not been possible in the conventional crosslinked acrylate-based hygroscopic fiber. The property that the solubility in dimethylformamide is 50% or less indicates that the composition has resistance to organic solvents. The characteristic that the solubility in a 1g/L sodium carbonate aqueous solution is 5% or less is expressed as a fiber having no intermolecular crosslinked structure due to covalent bonds and having a large number of highly hydrophilic carboxyl groups, and also being resistant to soaping treatment in washing and dyeing steps.
The amount of carboxyl groups in the modified acrylic fiber of the present invention is 0.2 to 4.0mmol/g, preferably 0.5 to 3.5mmol/g, and more preferably 1.0 to 3.5 mmol/g. If the amount of carboxyl groups does not satisfy the lower limit, sufficient moisture absorption performance may not be obtained, and if the amount exceeds the upper limit, the water-swelling property of the fiber may become too high, which is not preferable in practice.
When the hygroscopic property is regarded as important as the state of the carboxyl group, the counter ion is preferably a cation other than H. In the above case, examples of the cation include alkali metals such as Li, Na and K, alkaline earth metals such as Be, Ca and Ba, metals such as Cu, Zn, Al, Mn, Ag, Fe, Co and Ni, NH4And cations such as amines, and a plurality of cations may be present in combination. Among them, Li, Na, K, Mg, Ca, Zn and the like are suitable.
In addition, in the above case, excellent deodorizing performance can be exhibited against acid gases such as acetic acid and isovaleric acid, and aldehydes such as formaldehyde. Further, if Mg or Ca ions are used, the flame retardant property is high, and if Ag or Cu ions are used, the antibacterial property is high.
On the other hand, if the counter ion is H, that is, COOH, the state of the carboxyl group, excellent performance is exhibited particularly with respect to the deodorizing performance, antiviral performance, and antiallergic performance of amine-based gases such as ammonia, triethylamine, and pyridine.
When the modacrylic fiber of the present invention is used as a hygroscopic fiber, the saturated moisture absorption rate in an atmosphere of 20 ℃ and 65% relative humidity is preferably 3% by weight, more preferably 5% by weight, and still more preferably 10% by weight or more.
In the modacrylic fiber of the present invention, it is preferable that carboxyl groups are present throughout the entire fiber. Here, the term "present throughout the entire fiber" means that the coefficient of variation CV of the content ratio of magnesium element in the fiber cross section measured by the measurement method described later is 50% or less. In the modacrylic fiber of the present invention, as described above, the portion having a high carboxyl group concentration and the portion having a high nitrile group concentration are present throughout the entire fiber, so that embrittlement of the fiber due to moisture absorption and water absorption of the carboxyl groups can be suppressed, and the fiber can have physical properties that can withstand practical use even without having a crosslinked structure.
The modacrylic fibers of the present invention can be used alone or in combination with other materials as a fiber structure useful for various applications. The other materials are not particularly limited, and common natural fibers, organic fibers, semisynthetic fibers, synthetic fibers, and further inorganic fibers, glass fibers, and the like may be used depending on the application. Specific examples thereof include cotton, hemp, silk, wool, nylon, rayon, polyester, acrylic fibers and the like.
The appearance of the fiber structure includes: silk, nonwoven fabric, paper, sheet, laminate, cotton (including spherical and block), and the like. The fiber of the present invention contained in the structure may be mixed with other materials to form: substantially uniformly distributed; in the case of having a plurality of layers, the plural layers may be present collectively in any layer (may be singular or plural); distributed in a specific ratio in each layer, and the like.
The appearance and the content of the fiber structure, other materials constituting the fiber structure, and other members combined with the fiber structure can be appropriately determined in consideration of the contribution of the modacrylic fiber of the present invention to functions, characteristics, shapes, and modes for exhibiting the functions, which are required depending on the type of the final product (for example, clothing, filters, curtains, carpets, bedding, cushions, insoles).
Examples
The embodiments are described below to facilitate understanding of the present invention, but these are merely examples, and the gist of the present invention is not limited to these. In the examples, parts and percentages are by weight unless otherwise specified.
< determination of the amount of Total carboxyl groups >
After adding 1mol/l hydrochloric acid aqueous solution to the sample to adjust the pH to 2, the sample was washed with water, dried, and precisely weighed to obtain about 1g (W1 g), 200ml of water was added thereto, and the titration curve was determined by a conventional method using 0.1mol/l sodium hydroxide aqueous solution. From the titration curve, the consumption amount of the aqueous sodium hydroxide solution consumed for the carboxyl group (V1[ ml ]) was determined, and the amount of the carboxyl group was calculated by the following equation.
Amount of carboxyl group [ mmol/g ] ═ 0.1 XV 1/W1
< determination of solubility in aqueous sodium thiocyanate solution >
About 1g (W2 g) of the dried sample was precisely weighed, 100ml of a 58% aqueous solution of sodium thiocyanate was added, and the mixture was immersed at 80 ℃ for 1 hour, followed by filtration, washing with water and drying. The dried sample (W3 g) was precisely weighed, and the solubility was calculated by the following equation.
Solubility [% ] [ (-1-W3/W2) × 100
< determination of solubility in dimethylformamide >
The solubility was calculated in the same manner as the measurement of < solubility in aqueous sodium thiocyanate solution > except that the solution was changed to DMF and the immersion conditions were changed to 30 ℃ for 1 hour.
< determination of solubility in aqueous sodium carbonate solution >
The solubility was calculated in the same manner as in the measurement of < solubility in aqueous sodium thiocyanate solution > except that the solution was changed to aqueous sodium carbonate solution of 1g/L and the immersion conditions were changed to 95 ℃ for 30 minutes.
< measurement of saturated moisture absorption >
The sample was dried at 105 ℃ for 16 hours in a hot air dryer, and the weight (W4 g) was measured. Subsequently, the sample was placed in a thermostat adjusted to 20 ℃ x 65% RH for 24 hours. The weight (W5 g) of the thus-absorbed sample was measured. From the above measurement results, the following equation was used to calculate.
Saturated moisture absorption [% ] -W5-W4)/W4 × 100
< distribution of carboxyl groups in fiber Structure >
The fiber sample was immersed in an aqueous solution containing magnesium nitrate in an amount 2 times the amount of carboxyl groups contained in the fiber at 50 ℃ for 1 hour to carry out an ion exchange treatment, and then washed with water and dried to convert the counter ion of the carboxyl groups to magnesium. For a magnesium salt type fiber sample, 10 measurement points were selected at approximately equal intervals from the outer edge to the center of the fiber cross section by an energy dispersive X-ray spectrometer (EDS), and the content ratio of magnesium element in each measurement point was measured. From the values of the respective measurement points obtained, the coefficient of variation CV [% ] was calculated by the following formula.
Coefficient of variation CV [% ] [ (standard deviation/average value) × 100 [% ]
< measurement of moisture content of undried fiber after drawing >
The undried fibers after stretching were immersed in pure water, and then dehydrated for 2 minutes by a centrifugal dehydrator (TYPE H-770A, made by Kokai Kabushiki Kaisha) at a centrifugal acceleration of 1100G (G represents a gravitational acceleration). After the weight of the undried fiber after the dehydration was measured (W6), the undried fiber was dried at 120 ℃ for 15 minutes, and the weight was measured (W7) and calculated by the following formula.
Moisture content (%) of undried fiber after drawing (W6-W7)/W6 × 100
< example 1 >
A spinning dope in which 10 parts of an acrylonitrile polymer composed of 90% acrylonitrile and 10% methyl acrylate was dissolved in 90 parts of a 48% sodium thiocyanate aqueous solution was spun in a coagulation bath at-2.5 ℃ and coagulated, washed with water and stretched 12 times to obtain a gel-like acrylic fiber as a raw material having a water content of 35%. The fiber was immersed in a 1.0% aqueous sodium hydroxide solution and drawn, and then subjected to hydrolysis treatment at 123 ℃ for 25 minutes in a moist heat atmosphere, washed with water, and dried to obtain a modified acrylic fiber of the present invention. The evaluation results of the obtained fibers are shown in table 1.
< examples 2 to 6 >
The modacrylic fibers of the present invention were obtained in the same manner as in example 1 except that the concentration of the aqueous sodium hydroxide solution was changed to 2.5% in example 2, 7.5% in example 3, 10% in example 4, 15% in example 5, and 20% in example 6. The evaluation results of the obtained fibers are shown in table 1.
< examples 7 to 9 >
A modacrylic fiber of the present invention was obtained in the same manner as in example 3, except that in the formulation of example 3, instead of the 7.5% aqueous sodium hydroxide solution, a 7.5% aqueous potassium hydroxide solution was used in example 7, a 7.5% aqueous lithium hydroxide solution was used in example 8, and a 7.5% aqueous sodium carbonate solution was used in example 9. The evaluation results of the obtained fibers are shown in table 1.
< example 10 >
The modacrylic fibers of the present invention were obtained in the same manner as in example 1, except that the coagulation bath temperature was set to 10 ℃, the water content of the gel-like acrylic fiber was adjusted to 67%, and the concentration of the aqueous sodium hydroxide solution was changed to 3.8%. The evaluation results of the obtained fibers are shown in table 1.
< examples 11 and 12 >
The modacrylic fibers of the present invention were obtained in the same manner as in example 3, except that the temperature conditions for the hydrolysis treatment were set to 113 ℃ in example 11 and 135 ℃ in example 12. The evaluation results of the obtained fibers are shown in table 1.
< comparative example 1 >
The gel-like acrylic fiber obtained according to the formulation of example 1 was subjected to a heating treatment at 123 ℃ for 25 minutes in a moist heat atmosphere instead of the hydrolysis treatment with an aqueous sodium hydroxide solution, to obtain a fiber having no carboxyl group. The evaluation results of the obtained fibers are shown in table 1.
< comparative example 2 >
A spinning dope in which 10 parts of an acrylonitrile polymer composed of 92.5% acrylonitrile and 7.5% methacrylic acid was dissolved in 90 parts of a 48% sodium thiocyanate aqueous solution was spun by a conventional method, and after coagulation, washing with water, stretching, and drying, an acrylic fiber having a carboxyl group was obtained. The evaluation results of the obtained fibers are shown in table 1.
< comparative example 3 >
A spinning dope in which 10 parts of an acrylonitrile polymer composed of 85% acrylonitrile and 15% methacrylic acid was dissolved in 90 parts of a 48% sodium thiocyanate aqueous solution was spun by a conventional method, and then coagulated, washed with water, stretched and dried to obtain an acrylic fiber having a carboxyl group. The evaluation results of the obtained fibers are shown in table 1.
< comparative example 4 >
The fiber having no carboxyl group obtained in comparative example 1 was impregnated with an aqueous solution containing 0.5% hydrazine and 2% sodium hydroxide, and heat-treated at 115 ℃ for 2 hours to obtain a fiber having a crosslinked structure and a carboxyl group. The evaluation results of the obtained fibers are shown in table 1.
[ Table 1]
As shown in table 1, the modacrylic fibers of examples 1 to 12 obtained by the manufacturing method of the present invention have the following characteristics: has a carboxyl group content of 0.2 to 4.0mmol/g, has a solubility in a 58% aqueous solution of sodium thiocyanate of 95% or more, and has a solubility in dimethylformamide of 50% or less, or has a solubility in a 1g/L aqueous solution of sodium carbonate of 5% or less.
The fibers of comparative examples 2 and 3 obtained by copolymerizing a monomer having a carboxyl group were completely dissolved in dimethylformamide and were also soluble in an aqueous sodium carbonate solution. On the other hand, it was found that the modacrylic fibers of examples 3 and 4 having the same amount of carboxyl groups were not easily soluble in dimethylformamide nor in an aqueous solution of sodium carbonate.
Claims (8)
1. A modified acrylic fiber characterized by having 0.2 to 4mmol/g of carboxyl groups, having a solubility in a 58% aqueous solution of sodium thiocyanate of 95% or more and a solubility in dimethylformamide of 50% or less.
2. A modified acrylic fiber characterized by having 0.2 to 4mmol/g of carboxyl groups, having a solubility in a 58% aqueous sodium thiocyanate solution of 95% or more and a solubility in a 1g/L aqueous sodium carbonate solution of 5% or less.
3. The modified acrylic fiber according to claim 1 or 2, wherein the saturated moisture absorption rate at 20 ℃ x 65% RH is 3% or more.
4. The modacrylic fiber according to claim 1 or claim 2 wherein the carboxyl groups are present throughout the entire fiber.
5. The modacrylic fiber according to claim 3 wherein the carboxyl groups are present throughout the entire fiber.
6. A process for producing a modified acrylic fiber according to any one of claims 1 to 5, characterized in that a spinning dope in which an acrylic polymer is dissolved is spun from a nozzle, and then subjected to the steps of coagulation, washing with water and drawing to obtain an undried fiber, and the obtained undried fiber is hydrolyzed.
7. The process for producing a modacrylic fiber according to claim 6, wherein the moisture content of the undried fiber is 20 to 250%.
8. A fiber structure comprising the modacrylic fiber of any one of claims 1-5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/076815 WO2018047344A1 (en) | 2016-09-12 | 2016-09-12 | Modified acrylonitrile-based fiber, method for producing said fiber, and fibrous structure containing said fiber |
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| CN109689951A CN109689951A (en) | 2019-04-26 |
| CN109689951B true CN109689951B (en) | 2022-03-22 |
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| JP (1) | JP6819686B2 (en) |
| CN (1) | CN109689951B (en) |
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| WO2019058966A1 (en) * | 2017-09-22 | 2019-03-28 | 日本エクスラン工業株式会社 | Moisture absorbent acrylonitrile-based fiber, method for producing same and fiber structure containing same |
| JP7177982B2 (en) * | 2017-11-06 | 2022-11-29 | 日本エクスラン工業株式会社 | Hygroscopic acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7177986B2 (en) * | 2018-02-15 | 2022-11-25 | 日本エクスラン工業株式会社 | Shrinkable, moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7177987B2 (en) * | 2018-02-26 | 2022-11-25 | 日本エクスラン工業株式会社 | Easily de-crimpable and moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7177988B2 (en) * | 2018-03-09 | 2022-11-25 | 日本エクスラン工業株式会社 | Water-repellent and moisture-absorbing acrylonitrile-based fiber, method for producing said fiber, and fiber structure containing said fiber |
| JP7219418B2 (en) * | 2018-03-09 | 2023-02-08 | 日本エクスラン工業株式会社 | Crimped moisture-absorbing acrylonitrile fiber, method for producing said fiber, and fiber structure containing said fiber |
| CN111868322B (en) * | 2018-05-31 | 2023-03-14 | 日本爱克兰工业株式会社 | Beating acrylic fiber containing carboxyl group, process for producing the fiber, and structure containing the fiber |
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- 2016-09-12 WO PCT/JP2016/076815 patent/WO2018047344A1/en active Application Filing
- 2016-09-12 CN CN201680089157.3A patent/CN109689951B/en active Active
- 2016-09-12 JP JP2018537988A patent/JP6819686B2/en active Active
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2017
- 2017-08-01 TW TW106125803A patent/TWI727079B/en active
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| JPH11293516A (en) * | 1998-04-13 | 1999-10-26 | Mitsubishi Rayon Co Ltd | Superfine acrylic fiber having water absorption properties, its sheet-like product, and split acrylic fiber having water absorption properties |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI727079B (en) | 2021-05-11 |
| TW201816211A (en) | 2018-05-01 |
| JPWO2018047344A1 (en) | 2019-06-27 |
| CN109689951A (en) | 2019-04-26 |
| WO2018047344A1 (en) | 2018-03-15 |
| JP6819686B2 (en) | 2021-01-27 |
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