WO2018055868A1 - Fibre thermogène hygroscopique - Google Patents

Fibre thermogène hygroscopique Download PDF

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WO2018055868A1
WO2018055868A1 PCT/JP2017/024129 JP2017024129W WO2018055868A1 WO 2018055868 A1 WO2018055868 A1 WO 2018055868A1 JP 2017024129 W JP2017024129 W JP 2017024129W WO 2018055868 A1 WO2018055868 A1 WO 2018055868A1
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Prior art keywords
fiber
salt type
surface layer
cross
acrylonitrile
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PCT/JP2017/024129
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English (en)
Japanese (ja)
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宏 小野
成明 中村
正雄 家野
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東洋紡株式会社
日本エクスラン工業株式会社
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Application filed by 東洋紡株式会社, 日本エクスラン工業株式会社 filed Critical 東洋紡株式会社
Priority to JP2017551728A priority Critical patent/JP6247800B1/ja
Priority to KR1020197000081A priority patent/KR102334183B1/ko
Priority to CN201780048935.9A priority patent/CN109642349B/zh
Publication of WO2018055868A1 publication Critical patent/WO2018055868A1/fr

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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/08—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyacrylonitrile as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine

Definitions

  • the present invention relates to a moisture-absorbing exothermic fiber that has an initial temperature rise speed with respect to moisture-absorbing exothermic property, and has a high level of bulkiness and can quickly realize a warm environment comfortable to the human body. .
  • cross-linked acrylate fiber As a hygroscopic exothermic fiber, cross-linked acrylate fiber is most widely used in the clothing and industrial materials fields. Such cross-linked acrylate fibers are known to have harmonious functions such as pH buffering properties, antistatic properties, water retention, high moisture absorption rate, high moisture absorption rate, high moisture absorption rate difference, or temperature control / humidity control functions derived therefrom. (For example, Patent Documents 1 and 2).
  • the crosslinked acrylate fiber has a high moisture absorption rate, it has a feature that its bulkiness and form stability are lowered by the moisture absorbed. For this reason, card processing is difficult, and there has been a situation in which development for uses such as batting requires bulkiness.
  • a crosslinked acrylate system obtained by subjecting an acrylonitrile fiber having a side-by-side structure composed of two types of acrylonitrile polymers to a crosslinking treatment and a hydrolysis treatment with a nitrogen-containing compound.
  • a fiber was proposed (Patent Document 3).
  • This fiber has a hygroscopic exothermic property and bulkiness at a practical level, but because of its high bulkiness, it uses a polyvalent metal salt type cross-linked acrylate fiber such as Mg, Ca, etc.
  • Mg, Ca polyvalent metal salt type cross-linked acrylate fiber
  • JP 7-216730 A JP-A-5-132858 WO2015 / 041275
  • the present invention was devised in order to solve the problems of the prior art including Patent Document 3, and has an initial heat generation temperature rising speed with respect to moisture absorption heat generation, and has a high level of bulkiness. It is in providing the hygroscopic exothermic fiber which has.
  • the present inventor adopted Na salt type or K salt type as the crosslinked polyacrylate fiber to enhance the initial moisture absorption exothermic property, and Na salt type or K salt.
  • High bulkiness by compensating for low bulkiness, which is a defect of the mold, by adopting a specific composite structure with a small surface layer that expresses hygroscopic heat generation and a technology that increases the amount of carboxyl groups in the surface layer It was found that an initial high temperature rise due to moisture absorption exothermic property can be achieved while maintaining the above, and the present invention has been completed.
  • the center part Is a side-by-side structure consisting of two specific types of acrylonitrile-based polymers, and the surrounding layer that exhibits hygroscopic heat generation is made as small as possible to create a composite structure with increased bulkiness. Is performed under milder conditions with a lower concentration of alkali metal compound than before, and the subsequent acid treatment is performed under severer conditions at higher temperatures than in the past. It was found that sex can be expressed.
  • the graph which shows transition of the temperature for every elapsed time of the cross-linked polyacrylate type fiber of Na salt type or Mg salt type measured based on the measuring method and conditions of ISO18782: 2015 is shown in FIG.
  • the Na salt type is superior to the Mg salt type with respect to the initial rise temperature based on the hygroscopic exothermic property of the crosslinked polyacrylate fiber.
  • a composite fiber comprising a cross-linked structure and a surface layer portion having a Na salt type or K salt type carboxyl group, and a central portion of a side-by-side structure composed of two types of acrylonitrile-based polymers having different acrylonitrile content rates.
  • the moisture absorption is characterized in that the area occupied by the surface layer portion in the cross section of the composite fiber is 5% or more and less than 20%, and the saturated moisture absorption in an environment of 20 ° C. and relative humidity 65% is 20% or more.
  • Pyrogenic fiber is characterized in that the area occupied by the surface layer portion in the cross section of the composite fiber is 5% or more and less than 20%, and the saturated moisture absorption in an environment of 20 ° C. and relative humidity 65% is 20% or more.
  • the hygroscopic exothermic fiber of the present invention has an initial high elevated temperature due to hygroscopic exothermic properties, which cannot be achieved with conventional polyvalent metal salt type cross-linked polyacrylate fibers such as Mg salt type and Ca salt type. It has the effect of having a bulky level. Such an effect is brought about by the presence of hygroscopic exothermic property, a specific composite structure and a high concentration of carboxyl groups, which show a high temperature rise early in the Na salt type or K salt type cross-linked polyacrylate fiber.
  • the hygroscopic exothermic fiber of the present invention is capable of quickly absorbing a large amount of moist air taken in due to its high bulkiness and high hygroscopic exothermic property that quickly rises in temperature, and quickly transforming it into warm air of low humidity. Therefore, when used as a bedding or batting for autumn / winter outdoor clothing, the wearer can feel warmth and heat retention at an extremely fast stage.
  • the hygroscopic exothermic fiber of the present invention comprises a cross-linked structure and a surface layer part having a Na salt type or K salt type carboxyl group, and a central part of a side-by-side type structure composed of two types of acrylonitrile-based polymers having different acrylonitrile contents.
  • the area occupied by the surface layer portion in the cross section of the composite fiber is 5% or more and less than 20%, and the saturated moisture absorption in an environment of 20 ° C. and relative humidity 65% is 20% or more. It is characterized by that. Due to such characteristics, both moisture absorption exothermicity that quickly absorbs moisture and exhibits high exothermicity and bulkiness that provides sustained heat retention are provided at a high level.
  • the hygroscopic exothermic fiber of the present invention needs to be a crosslinked polyacrylate fiber having a monovalent metal Na salt type or K salt type carboxyl group.
  • Mg salt type or Ca salt type divalent metal salt type has high moisture absorption exothermic property and moderately high bulkiness, but since the initial rise temperature during moisture absorption exotherm is low, warmth and heat retention can be achieved early. There is a problem if you want to feel it.
  • other divalent metal salt types such as a Zn salt type are not preferable because they are inferior in hygroscopic heat generation and a comfortable environment cannot be obtained.
  • the monovalent metal salt type of the Na salt type or the K salt type has a high initial temperature rise during the hygroscopic heat generation, and thus can feel warmth at an early stage.
  • the Na salt type or K salt type cross-linked polyacrylate fiber has a special composite structure as described later in the present invention because the bulkiness is insufficient in the normal fiber form and the heat retention cannot be maintained.
  • the hygroscopic exothermic fiber of the present invention comprises a cross-linked structure and a surface layer part having a Na salt type or K salt type carboxyl group, and a central part of a side-by-side type structure composed of two types of acrylonitrile-based polymers having different acrylonitrile contents. It is necessary that the area occupied by the surface layer portion in the cross section of the composite fiber is 5% or more and less than 20%.
  • the hygroscopic exothermic fiber of the present invention has a composite structure consisting of a central portion and a surface layer portion around the central portion, and contributes to improvement in bulkiness by making a hard structure as large as possible in the central portion, and crosslinks at the surface layer portion.
  • the hygroscopic exothermic fiber of the present invention can have 3.5 mmol / g or more with respect to the total amount of carboxyl groups, and can be up to about 10 mmol / g. Actually, the entire amount of this carboxyl group is present in the surface layer portion. Further, it is possible to achieve 20% or more, further 30% or more with respect to the moisture absorption rate defined in the examples described later, and up to about 70% is possible.
  • the hygroscopic exothermic fiber of the present invention uses an acrylonitrile fiber as a raw fiber, and the acrylonitrile fiber can be produced from an acrylonitrile polymer by a known method.
  • the acrylonitrile polymer preferably has an acrylonitrile content of 50% by weight or more, more preferably 80% by weight or more. When the content of acrylonitrile is small, the cross-linked structure is reduced and the fiber properties may be deteriorated.
  • the crosslinked structure can be introduced into the fiber by reacting the nitrile group of the acrylonitrile polymer with a nitrogen-containing compound such as a hydrazine compound.
  • the hygroscopic exothermic fiber of the present invention has a composite structure in which two acrylonitrile polymers having different acrylonitrile contents are joined side by side.
  • a difference occurs in the degree of shrinkage during the hydrolysis treatment, and crimps can be expressed as a result. It can contribute to the improvement of bulkiness.
  • the difference in acrylonitrile content between the two acrylonitrile polymers is preferably 1 to 8% by weight, more preferably 1 to 5% by weight.
  • the composite ratio (weight ratio) of the acrylonitrile polymer is preferably 20/80 to 80/20, more preferably 30/70 to 70/30.
  • a cross-linked structure is introduced into the surface layer of the fiber having a composite structure as described above.
  • a conventionally known crosslinking agent may be used, but it is preferable to use a nitrogen-containing compound from the viewpoint of the introduction efficiency of the crosslinked structure.
  • the nitrogen-containing compound it is preferable to use an amino compound or a hydrazine compound having two or more primary amino groups.
  • amino compounds having two or more primary amino groups include diamine compounds such as ethylenediamine and hexamethylenediamine, diethylenetriamine, 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis ( Triamine compounds such as propylamine), triethylenetetramine, N, N′-bis (3-aminopropyl) -1,3-propylenediamine, N, N′-bis (3-aminopropyl) -1,4- Examples include tetramine compounds such as butylenediamine, polyvinylamine, polyallylamine, and the like, and polyamine compounds having two or more primary amino groups.
  • diamine compounds such as ethylenediamine and hexamethylenediamine, diethylenetriamine, 3,3′-iminobis (propylamine), N-methyl-3,3′-iminobis ( Triamine compounds such as propylamine), triethylenetetramine, N, N′-bis (3-aminopropy
  • hydrazine compound examples include hydrazine hydrate, hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrobromide, hydrazine carbonate, and the like.
  • the upper limit of the number of nitrogen atoms in one molecule is not particularly limited, but is preferably 12 or less, more preferably 6 or less, and particularly preferably 4 or less. When the number of nitrogen atoms in one molecule exceeds the above upper limit, the cross-linking agent molecule becomes large and it may be difficult to introduce a cross-linked structure into the fiber.
  • the conditions for introducing the cross-linked structure are not particularly limited, and can be appropriately selected in consideration of the reactivity between the cross-linking agent employed and the acrylonitrile fiber, the amount of the cross-linked structure, and the like.
  • a hydrazine compound is used as the cross-linking agent
  • the acrylonitrile fiber described above is immersed in an aqueous solution to which the hydrazine compound is added so that the hydrazine concentration is 0.1 to 10% by weight. And a method of treating at 2 ° C. for 2 to 10 hours.
  • hydrolysis treatment with an alkaline metal compound is performed, and nitrile groups present in the surface layer of the fiber are hydrolyzed to form carboxyl groups.
  • Specific treatment conditions may be set as appropriate in consideration of the amount of carboxyl groups described above, and the like, and various conditions such as the concentration of the treatment agent, reaction temperature, reaction time, etc. are preferably set, but preferably 0.5 to 10% by weight, More preferably, a means for treating in a 1 to 5% by weight treatment chemical aqueous solution at a temperature of 80 to 150 ° C. for 2 to 10 hours is preferred from the industrial and fiber viewpoints.
  • the above-described cross-linking introduction treatment and hydrolysis treatment are collectively performed simultaneously using an aqueous solution in which the respective treatment chemicals are mixed, rather than sequentially performing as described above.
  • the simultaneous treatment is performed under a milder condition of an alkali metal compound having a lower concentration than before, and the subsequent acid treatment is performed under severer conditions at a higher temperature than in the past.
  • the hygroscopic exothermic fiber of the present invention can have a structure in which more carboxyl groups are present in the narrow surface layer portion than before and a relatively hard acrylonitrile polymer is preserved in the center portion. .
  • the formed carboxyl group includes a salt-type carboxyl group whose counter ion is a cation other than a hydrogen ion, and an H-type carboxyl group whose counter ion is a hydrogen ion.
  • a salt-type carboxyl group whose counter ion is a cation other than a hydrogen ion
  • an H-type carboxyl group whose counter ion is a hydrogen ion In order to obtain a high moisture absorption rate, it is desirable that 50% or more of the carboxyl groups are salt-type carboxyl groups.
  • the cation constituting the salt-type carboxyl group is sodium or potassium alkali metal. When a polyvalent metal ion such as magnesium, calcium, or zinc is employed, the bulkiness is high, but the initial temperature rise due to moisture absorption is low, which is not preferable.
  • the hygroscopic exothermic fiber of the present invention is an acrylonitrile fiber in which two types of acrylonitrile polymers having different acrylonitrile contents are joined side by side under the conditions specific to the present invention as described above. It can be obtained by introducing a bridge and hydrolyzing to form a carboxyl group and selecting sodium or potassium as the counter ion.
  • Methods for adjusting the ratio of salt-type carboxyl groups to H-type carboxyl groups within the above range include ion exchange treatment with metal salts such as nitrates, sulfates and hydrochlorides, and acid treatments with nitric acid, sulfuric acid, hydrochloric acid, formic acid, etc.
  • metal salts such as nitrates, sulfates and hydrochlorides
  • acid treatments with nitric acid, sulfuric acid, hydrochloric acid, formic acid, etc Alternatively, a method of performing pH adjustment treatment with an alkaline metal compound or the like can be mentioned.
  • the area occupied by the surface layer portion in the cross section is 5% or more and less than 20%, preferably 10% or more and less than 20%.
  • the area of the surface layer portion is less than the above range, the carboxyl group cannot be sufficiently present in the fiber, and the high moisture absorption exothermic property cannot be exhibited.
  • the fibers tend to sag due to moisture absorption, causing a problem in bulkiness.
  • the area occupied by the surface layer of the fiber of the present invention is extremely small, and the area of the central part where the carboxyl group is substantially absent occupies a large area, so that the fiber sag due to moisture absorption, Na salt type or K salt type was adopted.
  • the influence of the decrease in bulkiness due to the is small, and high bulkiness can be achieved.
  • the Na salt-type or K-salt type cross-linked polyacrylate fiber has a high moisture absorption exothermic property (particularly, an initial rise temperature) as compared with a divalent metal salt such as an Mg salt type.
  • the features can be enjoyed as they are.
  • the hygroscopic exothermic fiber of the present invention is composed of the above-mentioned special composite structure Na salt type or K salt type cross-linked polyacrylate fiber, so that it is 6.0 within 5 minutes in an environment of 20 ° C. ⁇ 65% RH. Moisture absorption in the range of ⁇ 40% can be easily achieved.
  • the hygroscopic exothermic fiber of the present invention can realize a high hygroscopic exothermic effect (high temperature rise) within the first 5 minutes when human skin comes into contact.
  • the hygroscopic exothermic fiber of the present invention comprises the above-mentioned special composite structure Na salt type or K salt type cross-linked polyacrylate fiber, so that a specific volume in the range of 50 to 100 cm 3 / g is achieved. Can do. Such high bulkiness is brought about by the high bulkiness possessed by the special composite structure Na salt type or K salt type cross-linked polyacrylate fiber.
  • the specific volume is low, heat retention may not be sufficient because sufficient air is not taken in.
  • the specific volume is high, the shape may be easily lost by applying a little force, and the shape retention may be insufficient.
  • the hygroscopic exothermic fiber of the present invention can form a fiber structure by a conventionally known method alone or in combination with other materials. Appearance forms of such a fiber structure include cotton, yarn, knitted fabric, woven fabric, non-woven fabric, pile fabric, paper-like material, and the like.
  • the moisture-absorbing exothermic fiber of the present invention is contained in a form that is substantially uniformly distributed by mixing with other materials or in the case of a structure having a plurality of layers. Examples include a layer (one or plural) of which the hygroscopic exothermic fiber of the present invention is concentrated and the hygroscopic exothermic fiber of the present invention is distributed in a specific ratio in each layer.
  • Other materials that can be used in combination with the hygroscopic exothermic fiber of the present invention in the fiber structure include, for example, natural fibers, organic fibers, semi-synthetic fibers, synthetic fibers, and also inorganic fibers, glass fibers, etc. depending on the application. Can be adopted. Specific examples of the combination material include cotton, hemp, silk, wool, nylon, rayon, polyester, and acrylic fiber. In addition, the material used in combination may be a material such as feathers, resin, particles, and the like.
  • the fiber structure is batting
  • a combination with polyester is suitable.
  • a K salt type cross-linked polyacrylate fiber is a side-by-side type structure comprising a cross-linked structure and a surface layer portion having a Na salt type and / or K salt type carboxyl group, and two types of acrylonitrile polymers having different acrylonitrile contents.
  • a batting characterized in that the area occupied by the surface layer portion in the cross section of the composite fiber is 5% or more and less than 20%.
  • the hygroscopic exothermic fiber of the present invention can enjoy the advantages of hygroscopic exothermic heat and high bulkiness that can be realized at an early stage by using it together with other materials as necessary as a fiber structure. It has the comfort of being able to feel the warmth of low humidity that is not so early. For this reason, bedding (comforters, mattresses, pillows, etc.) or autumn / winter outer clothing using the moisture-absorbing and heat-generating fibers of the present invention immediately absorbs moisture released from the human body and quickly generates heat at a high temperature. It becomes warm, and it is possible to continuously feel the warmth due to the heat retention due to its high bulkiness.
  • (1) Amount of carboxyl group About 1 g of a fiber sample is immersed in 50 ml of a 1 mol / l hydrochloric acid aqueous solution for 30 minutes. The fiber sample is then immersed in water at a bath ratio of 1: 500. When it is confirmed that the bath pH is 4 or more after 15 minutes, the bath is dried (if the bath pH is less than 4, it is washed again with water). Next, about 0.2 g of a sufficiently dried fiber sample is precisely weighed (W1 [g]), 100 ml of water is added, and 15 ml of a 0.1 mol / l sodium hydroxide aqueous solution and 0.4 g of sodium chloride are added. And add phenolphthalein and stir.
  • the sample fiber is placed in a dyeing bath containing 2.5% cationic dye (Nichilon Black G 200) and 2% acetic acid with respect to the fiber weight, and the bath ratio is 1:80. After being soaked and boiled for 30 minutes, it is washed with water, dehydrated and dried. The obtained dyed fiber is sliced thinly perpendicular to the fiber axis, and the fiber cross section is observed with an optical microscope. At this time, the central portion made of the acrylonitrile-based polymer is dyed black, and the surface layer portion having many carboxyl groups becomes green because the dye is not sufficiently fixed.
  • the fiber diameter (D1) and the diameter (D2) of the center dyed black with the part starting to change from green to black as the boundary are measured, and the surface layer area ratio is calculated by the following formula To do.
  • the average value of the surface layer part area ratio of 10 samples be the surface layer part area ratio of a sample fiber.
  • Surface portion area ratio (%) [ ⁇ (( D1) / 2) 2 ⁇ - ((D2) / 2) 2 ⁇ / ((D1) / 2) 2 ⁇ ] ⁇ 100
  • the raw fiber was subjected to crosslinking introduction treatment and hydrolysis treatment simultaneously in an aqueous solution containing 0.5% by weight of hydrazine hydrate and 1.4% by weight of sodium hydroxide at 100 ° C. for 2 hours to obtain 8% by weight nitric acid.
  • the solution was treated with an aqueous solution at 120 ° C. for 3 hours and washed with water.
  • the obtained fiber is immersed in water, adjusted to pH 9 by adding sodium hydroxide, washed with water, and dried to form a Na salt type crosslinked polyacrylate fiber having a Na salt type carboxyl group (surface layer area 13%) )
  • the details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 2 In the same manner as in Example 1 except that the concentration of sodium hydroxide used for the cross-linking introduction / hydrolysis treatment was changed from 1.4% by weight to 1.2% by weight, Na salt-type cross-linked polyacrylate fiber (surface layer area 8) %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 3 In the same manner as in Example 1 except that the concentration of sodium hydroxide used for the crosslinking introduction / hydrolysis treatment was changed from 1.4% by weight to 1.6% by weight, the Na salt-type crosslinked polyacrylate fiber (surface layer area 18 %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 4 A K salt type crosslinked polyacrylate fiber (surface area 13%) was obtained by the same method except that potassium hydroxide was used instead of sodium hydroxide added to adjust to pH 9 in Example 1. The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 5 In the same manner as in Example 4 except that the concentration of potassium hydroxide used for the cross-linking introduction / hydrolysis treatment was changed from 1.4 wt% to 1.2 wt%, K salt type cross-linked polyacrylate fiber (surface layer area 8) %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 6 In the same manner as in Example 4 except that the concentration of potassium hydroxide used for the cross-linking introduction / hydrolysis treatment was changed from 1.4 wt% to 1.6 wt%, K salt type cross-linked polyacrylate fiber (surface layer area 18) %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 7 Na salt type crosslinked polyacrylate fibers were obtained in the same manner as in Example 1 except that the composition of the acrylonitrile polymer Ap was changed to 92% by weight of acrylonitrile and 8% by weight of methyl acrylate. The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 8 A Na salt type crosslinked polyacrylate fiber was obtained in the same manner as in Example 1 except that the composite ratio (weight ratio) of Ap / Bp was changed from 50/50 to 40/60. The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 9 A Na salt type crosslinked polyacrylate fiber was obtained in the same manner as in Example 1 except that the composite ratio (weight ratio) of Ap / Bp was changed from 50/50 to 60/40. The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 1 In the same manner as in Example 1, except that the concentration of sodium hydroxide used for the cross-linking introduction / hydrolysis treatment was changed from 1.4 wt% to 0.5 wt%, Na salt type cross-linked polyacrylate fiber (surface layer area 3) %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • Example 2 In the same manner as in Example 1 except that the concentration of sodium hydroxide used for the cross-linking introduction / hydrolysis treatment was changed from 1.4% by weight to 1.8% by weight, Na salt-type cross-linked polyacrylate fiber (surface layer area 25) %). The details and evaluation results of the obtained crosslinked polyacrylate fiber are shown in Table 1.
  • the raw fiber was subjected to crosslinking introduction treatment and hydrolysis treatment simultaneously in an aqueous solution containing 0.5% by weight of hydrazine hydrate and 1.4% by weight of sodium hydroxide at 100 ° C. for 2 hours to obtain 8% by weight nitric acid.
  • the solution was treated with an aqueous solution at 120 ° C. for 3 hours and washed with water.
  • the obtained fiber is immersed in water, adjusted to pH 9 by adding sodium hydroxide, and then immersed in an aqueous solution in which magnesium nitrate corresponding to twice the amount of carboxyl groups contained in the fiber is dissolved at 50 ° C. for 1 hour.
  • the raw fiber was subjected to crosslinking introduction treatment and hydrolysis treatment simultaneously in an aqueous solution containing 0.5% by weight of hydrazine hydrate and 1.4% by weight of sodium hydroxide at 100 ° C. for 2 hours to obtain 8% by weight nitric acid.
  • the solution was treated with an aqueous solution at 120 ° C. for 3 hours and washed with water.
  • the obtained fiber is immersed in water, adjusted to pH 9 by adding sodium hydroxide, and then immersed in an aqueous solution in which calcium nitrate corresponding to twice the amount of carboxyl groups contained in the fiber is dissolved at 50 ° C. for 1 hour.
  • the hygroscopic exothermic fibers of Examples 1 to 9 have both high hygroscopic exothermic properties (moisture absorption rate and rising temperature) and high bulkiness (specific volume), whereas Na salts Comparative Example 1 in which the surface layer part area of the type cross-linked polyacrylate fiber is small is inferior in hygroscopicity, and Comparative Example 2 in which the surface layer part area of the Na salt type cross-linked polyacrylate fiber is large is inferior in bulkiness, and Mg salt type cross-linking Comparative Examples 3 and 4 of the polyacrylate fiber had a problem of poor hygroscopicity. Moreover, the comparative example 5 of the Mg salt type
  • the hygroscopic exothermic fiber of the present invention has both high hygroscopic exothermic properties that can be realized at an early stage and high bulkiness that brings about heat retention, so that it can be comfortably used in bedding and clothing that touch human skin.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne une fibre thermogène hygroscopique, qui présente une augmentation de température initiale rapide liée à la génération de chaleur hygroscopique, et qui possède un niveau élevé d'encombrement. La fibre thermogène hygroscopique comprend : une partie couche de surface ayant une structure réticulée et un groupe carboxyle de type sel de Na ou sel de K ; et une partie âme qui a une structure côte à côte et est composée de deux types de polymères acrylonitrile ayant différents teneurs en acrylonitrile. La fibre thermogène hygroscopique est caractérisée en ce que la partie couche de surface occupe au moins 5 % et moins de 20 % de la surface d'une section transversale de la fibre composite, et en ce que le taux d'absorption d'humidité saturé est d'au moins 20 % dans un environnement dans lequel la température est de 20 °C et dans lequel l'humidité relative est de 65 %.
PCT/JP2017/024129 2016-09-26 2017-06-30 Fibre thermogène hygroscopique WO2018055868A1 (fr)

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Application Number Priority Date Filing Date Title
JP2017551728A JP6247800B1 (ja) 2016-09-26 2017-06-30 吸湿発熱性繊維
KR1020197000081A KR102334183B1 (ko) 2016-09-26 2017-06-30 흡습 발열성 섬유
CN201780048935.9A CN109642349B (zh) 2016-09-26 2017-06-30 吸湿发热性纤维

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JP2016-187321 2016-09-26
JP2016187321 2016-09-26

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WO2015041275A1 (fr) * 2013-09-20 2015-03-26 日本エクスラン工業株式会社 Fibre d'acrylate réticulé et structure de fibre contenant ladite fibre d'acrylate réticulé

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JP4674429B2 (ja) * 2001-09-18 2011-04-20 日本エクスラン工業株式会社 黒色高吸放湿性繊維
JP2006052489A (ja) * 2004-08-11 2006-02-23 Toho Tenax Co Ltd 吸湿性アクリル系繊維布帛及びその製造方法
JP5590341B2 (ja) * 2009-07-22 2014-09-17 日本エクスラン工業株式会社 酸性染料可染性吸湿性繊維およびその製造方法
JP6079981B2 (ja) * 2012-01-23 2017-02-15 日本エクスラン工業株式会社 抗インフルエンザウイルス用架橋アクリレート系繊維および該繊維を含有する抗インフルエンザウイルス用繊維構造物

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JPS5536360A (en) * 1978-09-05 1980-03-13 Japan Exlan Co Ltd Novel water-swelling fiber and its production
WO2015041275A1 (fr) * 2013-09-20 2015-03-26 日本エクスラン工業株式会社 Fibre d'acrylate réticulé et structure de fibre contenant ladite fibre d'acrylate réticulé

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