Method for continuously producing shape-memorized wool fiber product, and shape-memorized wool fiber product

Abstract

To provide a method for continuously producing a shape-memorized wool fiber product capable of continuously obtaining the shape-memorized wool fiber product.SOLUTION: There is provided a method for continuously producing a shape-memorized wool fiber product, the method including: a reduction step of treating a first precursor product containing wool fibers with a reduction treatment agent containing a water-soluble organic phosphine compound to obtain a second precursor product; a crosslinking step of treating the second precursor product with a cross-linking treatment agent containing an epoxy compound to obtain a third precursor product; an oxidation step of treating the third precursor product with an oxidation treatment agent containing both or either one of a persulfate and a hydrogen persulfate to obtain a fourth precursor product; a finishing step of washing the fourth precursor product with hot water and drying the product to obtain a shape-memorized wool fiber product, wherein the reduction step, the crosslinking step, the oxidation step and the finishing step are continuously performed in this order.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a continuous process for producing a shape-memory woolen textile product, and to a shape-memory woolen textile product. [Background technology]

[0002] Wool fiber products are excellent in soft texture, feel, moisture retention, etc., and are therefore used for various clothing applications such as sweaters, scarves, gloves, underwear, socks, etc. However, wool fiber products are known to deteriorate in quality with use due to the occurrence of a phenomenon called felt shrinkage, in which wool fibers shrink when washed, etc., and a phenomenon called pilling, in which fluff protruding from the surface of the product becomes entangled with each other due to friction, etc., and the like.

[0003] In order to prevent such quality deterioration, the Chroiharcossett method has been applied to wool fibers in which the edges of the scale-like cuticle are dissolved with chlorine and the remaining cuticle is covered with resin. This method has been shown to have a certain effect on felt shrinkage. Furthermore, Japanese Patent Laid-Open Publication No. 06-346369 (Patent Document 1) discloses a shrink-proofing method and agent for wool fibers that contain a water-soluble organic phosphine compound as an active ingredient. The above-mentioned Patent Document 1 states that pilling can be prevented by treating wool fiber products with an agent that contains a water-soluble organic phosphine compound as an active ingredient. Yukitake Wako, "Shape Memory Wool," Journal of Sen-i-Gakkaishi, Vol. 49, No. 7 (1993), pp. 249-251 (Non-Patent Document 1), teaches shape-memory wool in which the disulfide bonds of cystine contained in wool or animal hair are cleaved with a reducing agent such as thioglycolic acid, collagen protein derivatives are adsorbed onto the cleaved intermolecular chains, and then the disulfide bonds are rebonded with an oxidizing agent such as hydrogen peroxide. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 06-346369 [Non-patent literature]

[0005] [Non-Patent Document 1] Yukitake Wako, "Shape Memory Wool", Journal of the Society of Fiber Science and Technology, Vol. 49 (1993) No. 7, pp. 249-251 Summary of the Invention [Problem to be solved by the invention]

[0006] The soft texture, touch, and good moisture retention of wool fibers are considered to be properties based on the crimped appearance of the wool fibers themselves. On the other hand, the Chloyharcosset method dissolves the edge of the epidermis with chlorine as described above, and covers the remaining epidermis with resin, which embrittles the wool fibers and acts in the direction of eliminating crimp, and therefore has the drawback of impairing the soft texture, touch, etc. of the product. The wool fiber product disclosed in the above Patent Document 1 crosslinks the disulfide bonds of cystine cleaved by a water-soluble organic phosphine compound in wool and animal hair with the ether bonds based on epoxy compounds only, so it may not be sufficient to continuously obtain a soft texture, touch, etc. In addition, since it is a discontinuous manufacturing method, it is difficult to efficiently obtain wool fiber products. According to the reproduction experiment by the present inventors, the shape-memory wool taught in Non-Patent Document 1 was evaluated as not sufficient to obtain the soft texture, touch, etc. of wool products. Therefore, a continuous manufacturing method for shape-memory wool fiber products that can continuously and efficiently produce wool fiber products that can sustainably obtain soft texture, feel, and good moisture retention has not been realized, and its development is eagerly awaited.

[0007] In view of the above circumstances, an object of the present invention is to provide a method for continuously producing a shape-memory wool fiber product, which can continuously produce a shape-memory wool fiber product, and a shape-memory wool fiber product. [Means for solving the problem]

[0008] In the process of creating a shape-memorized wool fiber product that can maintain its soft texture, touch, etc. and can be obtained continuously and efficiently, the inventors focused on treating the wool fiber with a reducing agent without applying any special pressure to the wool fiber. They found that this allows wool fiber products to be obtained continuously and efficiently. They also found that the disulfide bonds cleaved by cystine can be directly recombined by crosslinking the wool fiber treated with a reducing agent with an epoxy compound and then oxidizing the same with an oxidizing agent containing both or either one of a persulfate and a hydrogen persulfate. Based on these findings, they continuously obtained wool fiber products from the wool fiber, and arrived at a wool fiber product that can maintain its soft texture, touch, etc. by shape memory, thereby completing the present invention. The present invention is specifically as follows.

[0009] [1] The method for continuously producing a shape-memory wool fiber product according to the present invention includes a reduction step of treating a first precursor product containing wool fibers with a reducing treatment agent containing a water-soluble organic phosphine compound to obtain a second precursor product, a crosslinking step of treating the second precursor product with a crosslinking treatment agent containing an epoxy compound to obtain a third precursor product, an oxidation step of treating the third precursor product with an oxidation treatment agent containing both or either one of a persulfate and a hydrogen persulfate to obtain a fourth precursor product, and a finishing step of washing the fourth precursor product with hot water and drying it to obtain a shape-memory wool fiber product, and the reduction step, crosslinking step, oxidation step, and finishing step are performed continuously in this order. [2] The processing time for each of the reduction step, the crosslinking step, the oxidation step, and the finishing step is preferably less than 10 minutes. [3] In the oxidation step, the persulfate and / or hydrogen persulfate are preferably used in a total amount of 0.001% by mass or more and 0.5% by mass or less based on the mass of the third precursor product. [4] The mass of the epoxy compound is preferably 10 to 50 times the sum of the mass of the persulfate and the hydrogen persulfate. [5] The wool fiber is preferably a spun yarn or wool TOP having a fiber diameter of 13.5 μm or more and 33 μm or less. [6] When the wool fiber is the spun yarn, it is preferable to knit the yarn into a tubular shape and arrange 5 to 20 of the tubular shapes in parallel to carry out the reduction step, the crosslinking step, and the oxidation step; when the wool fiber is the wool TOP, it is preferable to arrange 6 to 40 of the wool TOP in parallel to carry out the reduction step, the crosslinking step, and the oxidation step. [7] When the wool fiber is a wool TOP, it is preferable to carry out the reducing step in a folded state of the wool TOP. [8] The shape-memorizing wool fiber product according to the present invention is a shape-memorizing wool fiber product containing wool fibers, the wool fibers having an edge of a skin that is not melted, and the skin is not coated with a resin, and an image formed on a plane by projecting the wool fiber product 15g perpendicularly to the plane has a size of 225 cm. 2 It has an area of ​​more than 100m2. Effect of the Invention

[0010] According to the present invention, it is possible to provide a method for continuously producing a shape-memorized wool fiber product, which can continuously obtain a shape-memorized wool fiber product, and a shape-memorized wool fiber product. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a flow chart showing an example of a method for continuously producing a shape-memory wool fiber product according to the present embodiment. [Diagram 2] FIG. 2 is a photograph, substituted for a drawing, showing an image taken by a scanning electron microscope of the edge of the epidermis of a wool fiber contained in a wool fiber product to which the Croy-Harcossett method is applied. [Diagram 3]FIG. 3 is a photograph, substituted for a drawing, showing an image of the edge of the skin of a wool fiber contained in the shape-memory wool fiber product according to this embodiment, taken by a scanning electron microscope. [Figure 4] FIG. 4 is a photograph showing the wool tops of sample 1 and sample A arranged side by side to illustrate the soft feel of the shape-memory wool top of sample 1. FIG. [Diagram 5] FIG. 5 is a photograph showing the wool tops of sample 1 and sample B arranged side by side to illustrate the soft feel of the shape-memory wool top of sample 1. [Figure 6] FIG. 6 is a photograph showing the wool tops of sample 1 and sample C arranged side by side to illustrate the soft feel of the shape-memory wool top of sample 1. [Figure 7] FIG. 7 is a photograph showing the wool tops of sample 1 and sample D arranged side by side to illustrate the soft feel of the shape-memory wool top of sample 1. FIG. [Figure 8] Figure 8 is a photograph in lieu of a drawing showing images of knitted fabrics made from the wool tops of sample 1 and sample C arranged side by side to illustrate the soft texture of the knitted fabric made from the shape-memory wool top of sample 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention (hereinafter also referred to as "the present embodiment") will be described in more detail. In this specification, the expression in the form of "A to B" means the upper and lower limits of a range (i.e., A or more and B or less). It should be noted that when no unit is stated for A and a unit is stated only for B, the unit of A and the unit of B are the same.

[0013] [Continuous manufacturing method for shape-memorized wool fiber products] The continuous manufacturing method of the shape-memorized wool fiber product according to the present embodiment includes a reduction step of treating a first precursor product containing wool fibers with a reduction treatment agent containing a water-soluble organic phosphine compound to obtain a second precursor product, a crosslinking step of treating the second precursor product with a crosslinking treatment agent containing an epoxy compound to obtain a third precursor product, an oxidation step of treating the third precursor product with an oxidation treatment agent containing both or either one of a persulfate and a hydrogen persulfate to obtain a fourth precursor product, and a finishing step of washing the fourth precursor product with hot water and drying to obtain a shape-memorized wool fiber product. The continuous manufacturing method includes the reduction step, the crosslinking step, the oxidation step, and the finishing step in this order. The continuous manufacturing method of the shape-memorized wool fiber product having such characteristics can continuously and efficiently obtain a shape-memorized wool fiber product that can continuously obtain a soft texture, etc. It is particularly preferable that the processing times of the reduction step, the crosslinking step, the oxidation step, and the finishing step are all less than 10 minutes. This makes it possible to more efficiently obtain the shape-memorized wool fiber product.

[0014] In this specification, "wool" refers to a general term for wool yarn obtained from sheep. The above-mentioned "wool" may be dyed in advance. In this specification, "wool fiber" refers to each fiber constituting the above-mentioned wool. "Wool fiber product" refers to a felt which is a nonwoven fabric of the above-mentioned wool fiber, or a product obtained by weaving, knitting or sewing the above-mentioned wool fiber. "Wool fiber product" specifically refers to clothing in the form of the above-mentioned felt, or in the form of woven fabric, knitting or sewing, and more specifically, sweaters, vests, cardigans, mufflers, scarves, stoles, gloves, socks, underwear, underwear, etc. are exemplified. However, in this specification, the category of "wool fiber product" also includes wool TOP, spun yarn, worsted and spun wool. In addition, "wool fiber product" includes products woven, knitted or sewn by "blending" of the above-mentioned wool and synthetic fibers, as long as it does not deviate from the effect of the present invention. The above-mentioned "TOP" refers to a yarn obtained by dyeing a bundle of fibers in an appropriate color and then spinning the bundle.

[0015] In this specification, the term "first precursor product" refers to a wool fiber product in a state before the continuous manufacturing method of the shape-memorized wool fiber product of the present invention is carried out. More specifically, it refers to a TOP itself, a spun yarn itself, a worsted yarn itself, or a woolen yarn itself to which the Croy-Harcossett method is not applied, or a fiber product produced by weaving, knitting, or sewing one selected from the group consisting of the TOP, the spun yarn, the worsted yarn, the woolen yarn, and other woolen spun yarns alone or in combination by a conventionally known method, and refers to a wool fiber product before the continuous manufacturing method of the shape-memorized wool fiber product of the present invention is carried out. The term "second precursor product" refers to a product obtained by the reduction step, and particularly refers to a fiber product in which some or all of the disulfide bonds of cystine are cleaved in the epidermis of the wool fiber in the product. The term "third precursor product" refers to a product obtained by the above-mentioned crosslinking step, and in particular refers to a textile product in which some of the cystine whose disulfide bonds have been cleaved in the epidermis of the wool fibers in the product are crosslinked with each other by an epoxy compound. The term "fourth precursor product" refers to a product obtained by the above-mentioned oxidation step, and in particular refers to a textile product in which some or all of the disulfide bonds of the cystine that have been cleaved in the epidermis of the wool fibers in the product are rebonded. Hereinafter, with reference to FIG. 1, each step included in the continuous manufacturing method for a shape-memory wool fiber product according to this embodiment will be described in order of steps. FIG. 1 is a flow chart showing an example of the continuous manufacturing method for a shape-memory wool fiber product according to this embodiment.

[0016] <Reduction process> As shown in FIG. 1, the continuous manufacturing method of shape-memory wool fiber products according to this embodiment includes a reduction step S10 in which a first precursor product containing wool fibers is treated with a reducing agent containing a water-soluble organic phosphine compound to obtain a second precursor product. The reduction step S10 is a step in which the first precursor product containing wool fibers is reduced with a water-soluble organic phosphine compound for the purpose of cleaving disulfide bonds of cystine contained in the epidermis of the wool fibers. Specifically, in the reduction step S10, it is preferable to immerse the first precursor product in a water bath at 20 to 100°C containing the water-soluble organic phosphine compound for 1 minute or more and less than 10 minutes, and to allow the water-soluble organic phosphine compound to act on the first precursor product. This is believed to promote cleavage of disulfide bonds of cystine in the scaly epidermis of the wool fibers. Furthermore, by allowing the water-soluble organic phosphine compound to act on the first precursor product, cleavage of salt bonds (ionic bonds) and hydrogen bonds in the epidermis of the wool fibers can also be promoted. The water-soluble organic phosphine compound may also have the effect of swelling the scaly epidermis of wool fibers. These effects turn the first precursor product into the second precursor product, preparing the conditions for the oxidation treatment agent to act in the oxidation step described below.

[0017] The wool fiber is preferably a spun yarn or wool TOP having a fiber diameter of 13.5 μm or more and 33 μm or less. When the wool fiber is a spun yarn or wool TOP having a fiber diameter in the above range, a shape-memorizing wool fiber product can be obtained with a higher yield. When the wool fiber is a spun yarn, the fiber diameter is preferably 15 to 25 μm. When the wool fiber is a wool TOP, the fiber diameter is preferably 15 to 25 μm.

[0018] When the wool fiber is the spun yarn, it is preferable to perform the reduction step S10 by arranging the spun yarn in a tubular knit and arranging 5 to 20 of the tubular knit in parallel. When the wool fiber is the wool TOP, it is preferable to perform the reduction step S10 by arranging 6 to 40 of the wool TOP in parallel. Furthermore, when the wool fiber is the wool TOP, it is preferable to perform the reduction step S10 in a folded state. This makes it possible to reduce the amount of water and chemicals used in the reduction step S10. Furthermore, it is possible to increase the amount of the first precursor product processed per hour. In the reduction step S10, specifically, it is preferable that the first precursor product including the wool fiber made into the spun yarn or the wool TOP is introduced into a water bath in which the reduction treatment agent is dissolved using a conventionally known roller or the like in a state where a plurality of pieces are arranged in parallel as described above, and then reduced in the water bath.

[0019] The mass of the water-soluble organic phosphine compound added to the water bath is preferably 0.1 to 3% owf (% owf represents a percentage relative to the fiber mass) in terms of the atomic weight of phosphorus relative to the fiber mass of the first precursor product, and more preferably 0.3 to 1% owf. The concentration of the water-soluble organic phosphine compound in the water bath is preferably 5 to 20 g per 1 liter of water as a guideline. If the concentration is within this guideline range, the water-soluble organic phosphine compound overlaps with the range of the added mass expressed in terms of the atomic weight of phosphorus described above, so that the cleavage of the disulfide bond of cystine in the scaly epidermis of wool fibers can be easily promoted. If the concentration of the water-soluble organic phosphine compound in the water bath is less than 5 g per 1 liter of water, the action of the water-soluble organic phosphine compound tends to be insufficient. If the concentration of the water-soluble organic phosphine compound in the water bath exceeds 20 g per 1 liter of water, it tends to be economically inefficient. The usage ratio (bath ratio) of the water bath containing the water-soluble organic phosphine compound to the first precursor product is preferably 1 to 20 times, more preferably 2 to 10 times, and most preferably 3 to 7 times the mass of the first precursor product.

[0020] Furthermore, the temperature of the water bath in which the reducing agent acts on the first precursor product is preferably 30 to 90°C, more preferably 60 to 80°C. The time for which the reducing agent acts is preferably 1 minute or more and less than 10 minutes. If the temperature of the water bath is 20°C or less, the action of the water-soluble organic phosphine compound tends not to be fully exerted. If the temperature of the water bath exceeds 100°C, the high temperature tends to make it difficult to manage the reduction step S10. If the time for which the reducing agent acts is less than 1 minute, the action of the water-soluble organic phosphine compound tends not to be fully exerted. If the time for which the reducing agent acts is 10 minutes or more, the reduction step S10 tends not to be performed efficiently. If the temperature of the water bath is within the above-mentioned range, the lower the temperature (for example, 30°C), the longer the time for which the reducing agent acts (for example, about 9 minutes and 50 seconds), and the higher the temperature (for example, 80°C), the shorter the time for which the reducing agent acts (for example, 1 to 5 minutes).

[0021] As the water-soluble organic phosphine compound, any compound that falls into this category can be used without any particular limitation, so long as it is water-soluble and is a solid or liquid at room temperature. The water-soluble organic phosphine compound can exhibit water solubility as a whole by containing a hydrophilic group, such as a hydroxyl group, a carboxyl group, a sulfone group, a hydroxylamino group, or a hydroxymethyl group, as an organic group bonded to a phosphorus atom in the molecule.

[0022] Examples of the water-soluble organic phosphine compound include dimethylhydroxymethylphosphine, dimethylhydroxyethylphosphine, ethylbis(hydroxyethyl)phosphine, ethylbis(hydroxypropyl)phosphine, tris(hydroxymethyl)phosphine, tris(hydroxyethyl)phosphine, tris(hydroxypropyl)phosphine, tris(hydroxyoctyl)phosphine, tris(hydroxycyclohexyl)phosphine, tris(hydroxybutyl)phosphine, tris(hydroxyphenyl)phosphine, and the like. The water-soluble organic phosphine compound may further be an alkylene oxide adduct such as an ethylene oxide adduct, a propylene oxide adduct, or an ethylene oxide and propylene oxide adduct. The number of moles of the alkylene oxide adduct is not particularly limited, but is usually 1 to 20, preferably 1 to 10. The water-soluble organic phosphine compound may be one selected from the group consisting of the above-mentioned compounds, or two or more of them may be used in combination. As the water-soluble organic phosphine compound, for example, tris(hydroxypropyl)phosphine (product name: "Hishicolin P-540 (PP-40)", manufactured by Nippon Chemical Industry Co., Ltd.) can be preferably used.

[0023] The second precursor product obtained by the reduction step S10 is preferably taken out of the water bath in which the reducing agent is dissolved, and after dehydration, etc., introduced into the water bath in which the crosslinking agent is dissolved using a conventionally known roller, etc., and the crosslinking step described below is carried out. In this way, the wool fiber product (specifically, the second precursor product) can be transported from the water bath in which the reduction step S10 is carried out to the water bath in which the crosslinking step is carried out, thereby enabling continuous processing.

[0024] <Crosslinking process> The continuous manufacturing method of the shape-memorized wool fiber product according to the present embodiment includes a crosslinking step S20 in which the second precursor product is treated with a crosslinking agent containing an epoxy compound to obtain a third precursor product. The crosslinking step S20 aims to crosslink some of the cystine in the epidermis of the wool fiber contained in the second precursor product, in which the disulfide bonds in the epidermis are cleaved, with each other using an epoxy compound. This can promote the recombination of the disulfide bonds in the oxidation step described below, and thus makes it easier to obtain a fourth precursor product that is endowed with the performance of shape memory. Specifically, in the crosslinking step S20, it is preferable to immerse the second precursor product obtained in the reduction step S10 in a water bath at 10 to 60°C in which a crosslinking agent containing an epoxy compound is dissolved for 1 minute or more and less than 10 minutes, and to allow the crosslinking agent to act on the second precursor product. A shape-memorized wool fiber product can be obtained from the third precursor product obtained in the crosslinking step S20 through the oxidation step and finishing step described below.

[0025] Here, when the wool fiber is the spun yarn, it is preferable to carry out the crosslinking step S20 by arranging the spun yarn into a tube knitted yarn and arranging 5 to 20 of the tube knitted yarns in parallel after the reduction step S10. When the wool fiber is the wool TOP, it is preferable to carry out the crosslinking step S20 by arranging 6 to 40 of the wool TOPs in parallel after the reduction step S10. This makes it possible to reduce the amount of water and chemicals used in the crosslinking step S20. Furthermore, it is possible to increase the amount of the second precursor product processed per hour. In the crosslinking step S20, specifically, it is preferable that the second precursor product including the wool fiber made into the spun yarn or the wool TOP, in a state where a plurality of pieces are arranged in parallel as described above, is introduced into a water bath in which the crosslinking agent is dissolved using a conventionally known roller or the like, and then crosslinked in the water bath.

[0026] In the crosslinking step S20, it is preferable to use the epoxy compound in an amount of 0.1% by mass or more and 10% by mass or less based on the mass of the second precursor product. It is more preferable that the amount of the epoxy compound used is 0.2% by mass or more and 5% by mass or less based on the mass of the second precursor product. This allows the crosslinking treatment of the second precursor product to proceed efficiently.

[0027] In the crosslinking step S20, the mass of the epoxy compound added to the water bath is preferably 0.5 to 15% owf, more preferably 1 to 8% owf, in terms of the atomic weight of oxygen, relative to the fiber mass of the second precursor product. As a guideline, the concentration of the epoxy compound in the water bath is preferably 1 to 10 g per liter of water, more preferably 2 to 8 g per liter of water, and most preferably 3 to 6 g per liter of water. If the concentration is within this guideline, the epoxy compound overlaps with the range of the added mass shown in terms of the atomic weight of oxygen described above, so that the crosslinking of cystine resulting from the cleavage of the disulfide bond in the epidermis of the wool fiber can be easily promoted. If the concentration of the epoxy compound in the water bath is less than 1 g per liter of water, the effect of the epoxy compound tends to be insufficient. If the concentration of the epoxy compound in the water bath exceeds 10 g per liter of water, it tends to be economically inefficient. The usage ratio (bath ratio) of the water bath containing the epoxy compound to the second precursor product is preferably 1 to 20 times the mass of the water bath relative to the mass of the second precursor product, more preferably 2 to 10 times, and most preferably 3 to 7 times.

[0028] Furthermore, the temperature of the water bath in which the crosslinking agent acts on the second precursor product is preferably 10 to 60°C, more preferably 20 to 50°C. The time for which the crosslinking agent acts is preferably 1 minute or more and less than 10 minutes. If the temperature of the water bath is 10°C or less, the action of the epoxy compound tends not to be fully exerted. If the temperature of the water bath exceeds 60°C, the crosslinking step S20 tends to be economically inefficient. If the time for which the crosslinking agent acts is less than 1 minute, the action of the epoxy compound tends not to be fully exerted. If the time for which the crosslinking agent acts exceeds 10 minutes, the crosslinking step S20 tends to be economically inefficient. If the temperature of the water bath is within the above-mentioned range, the lower the temperature (for example, 20°C), the longer the time for which the crosslinking agent acts (for example, about 9 minutes and 50 seconds), and the higher the temperature (for example, 60°C), the shorter the time for which the crosslinking agent acts (for example, 1 to 5 minutes).

[0029] The epoxy compound may be one or more selected from the group consisting of monoepoxy compounds and polyfunctional epoxy compounds. More specifically, a monofunctional glycidyl ether compound or a polyfunctional glycidyl ether compound having two or more functionalities may be used. In particular, a bifunctional diglycidyl ether compound is preferred, specifically ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcinol diglycidyl ether, and hydroquinone diglycidyl ether are preferred. Furthermore, glycerol triglycidyl ether, 2,2-bis(bromomethyl)propylene glycol diglycidyl ether, lauryl alcohol ethylene oxide adduct glycidyl ether, sorbitan polyglycidyl ether, neopentyl glycol diglycidyl ether, and the like may also be used. The epoxy compound may be one selected from the group consisting of the above-mentioned compounds, or two or more may be used in combination.

[0030] As the epoxy compound, it is most preferable to use ethylene glycol diglycidyl ether (product name: "Epolite 40E" manufactured by Kyoeisha Chemical Co., Ltd., or product name: "Denacol EX810" manufactured by Nagase ChemteX Corporation). The third precursor product obtained by the crosslinking step S20 is taken out of the water bath in which the crosslinking treatment agent is dissolved, dehydrated, and then introduced into the water bath in which the oxidation treatment agent is dissolved using a conventionally known roller or the like, and the oxidation step described below is preferably carried out. In this way, the wool fiber product (specifically, the third precursor product) can be transported from the water bath in which the crosslinking step S20 is carried out to the water bath in which the oxidation step is carried out, thereby enabling continuous treatment.

[0031] <Oxidation process> The continuous manufacturing method of the shape-memory wool fiber product according to the present embodiment includes an oxidation step S30 in which the third precursor product is treated with an oxidation treatment agent containing both or either one of a persulfate and a hydrogen persulfate to obtain a fourth precursor product. According to the oxidation step S30, by treating the third precursor product with both or either one of a persulfate and a hydrogen persulfate, a part or all of the disulfide bonds of the cleaved cystine in the epidermis of the wool fiber contained in the third precursor product can be recombined, thereby obtaining a fourth precursor product having a shape memory property. Specifically, in the oxidation step S30, it is preferable to immerse the third precursor product obtained in the crosslinking step S20 in a water bath at 10 to 60°C in which an oxidation treatment agent containing both or either one of a persulfate and a hydrogen persulfate is dissolved for 1 minute or more and less than 10 minutes, and to allow the oxidation treatment agent to act on the third precursor product. A shape-memorized wool fiber product can be obtained from the fourth precursor product obtained in the oxidation step S30 by passing through a finishing step described below.

[0032] Here, when the wool fiber is the spun yarn, it is preferable to carry out the oxidation step S30 by arranging the spun yarn into a cylindrical knitted yarn and arranging 5 to 20 cylindrical knitted yarns in parallel after the reduction step S10 and the crosslinking step S20. When the wool fiber is the wool TOP, it is preferable to carry out the oxidation step S30 by arranging 6 to 40 wool TOPs in parallel after the reduction step S10 and the crosslinking step S20. This makes it possible to reduce the amount of water and chemicals used in the oxidation step S30. Furthermore, it is possible to increase the amount of the third precursor product processed per hour. In the oxidation step S30, specifically, it is preferable that the third precursor product including the wool fiber made into the spun yarn or the wool TOP, in a state where a plurality of pieces are arranged in parallel as described above, is introduced into a water bath in which the oxidation treatment agent is dissolved using a conventionally known roller or the like, and then oxidized in the water bath.

[0033] In the oxidation step S30, the total amount of the persulfate and / or hydrogen persulfate is preferably 0.001% by mass to 0.5% by mass relative to the mass of the third precursor product. The total amount of the persulfate and / or hydrogen persulfate is more preferably 0.01% by mass to 0.1% by mass relative to the mass of the third precursor product. In particular, the mass of the epoxy compound is preferably 10 times to 50 times the sum of the masses of the persulfate and hydrogen persulfate constituting the oxidation treatment agent. The mass of the epoxy compound is more preferably 20 times to 30 times the sum of the masses of the persulfate and hydrogen persulfate.

[0034] In the oxidation step S30, the mass of both or either of the persulfate and hydrogen persulfate added to the water bath is preferably 0.0105-5.26% owf, more preferably 0.105-0.526% owf, in terms of the atomic weight of oxygen, relative to the fiber mass of the third precursor product. As a guideline, the mass of both or either of the persulfate and hydrogen persulfate is preferably 0.02-10g per 1 liter of water, more preferably 0.1-5g per 1 liter of water, and most preferably 0.2-1g per 1 liter of water, in the water bath. If the concentration is within this guideline range, both or either of the persulfate and hydrogen persulfate overlaps with the range of the added mass shown in terms of the atomic weight of oxygen, so that the recombination of the disulfide bond of cystine in the epidermis of wool fiber can be easily promoted. When the concentration of the persulfate and / or hydrogen persulfate in the water bath is less than 0.1 g per liter of water, the action of the persulfate and / or hydrogen persulfate tends to be insufficient. When the concentration of the persulfate and / or hydrogen persulfate in the water bath exceeds 10 g per liter of water, the process tends to be economically inefficient. The ratio (bath ratio) of the water bath containing the oxidation treatment agent to the third precursor product is preferably 1 to 20 times the mass of the third precursor product, more preferably 2 to 10 times, and most preferably 3 to 7 times.

[0035] Furthermore, the temperature of the water bath in which the oxidation treatment agent is applied to the third precursor product is preferably 10 to 60°C, and more preferably 20 to 50°C. The time for applying the oxidation treatment agent is preferably 1 minute or more and less than 10 minutes. If the temperature of the water bath is 10°C or less, the action of both or either of the persulfate and hydrogen persulfate tends to be insufficient. If the temperature of the water bath exceeds 60°C, the oxidation step S30 tends to be economically inefficient. If the time for applying the oxidation treatment agent is less than 1 minute, the action of both or either of the persulfate and hydrogen persulfate tends to be insufficient. If the time for applying the oxidation treatment agent exceeds 10 minutes, the oxidation step S30 tends to be economically inefficient. If the temperature of the water bath is within the above-mentioned range, the lower the temperature (for example, 20°C), the longer the time for applying the oxidation treatment agent (for example, about 9 minutes and 50 seconds) is preferable, and the higher the temperature (for example, 60°C), the shorter the time for applying the oxidation treatment agent (for example, 1 to 5 minutes) is preferable.

[0036] As the persulfate and / or hydrogen persulfate constituting the oxidation treatment agent, from the viewpoint of effectively recombining the cleaved disulfide bonds of cystine contained in the scaly epidermis of wool fibers, for example, peroxymonosulfate and / or hydrogen peroxodisulfate can be used. In this embodiment, from the viewpoints of ease of availability and economic efficiency, it is most preferable to use potassium peroxymonosulfate (product name: "Oxone", manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as the persulfate and / or hydrogen persulfate constituting the oxidation treatment agent.

[0037] The fourth precursor product obtained in the oxidation step S30 is taken out of the water bath in which the oxidation treatment agent is dissolved, dehydrated, and then continuously introduced into a water bath filled with hot water (40 to 100°C) using a conventionally known roller or the like. This makes it ready for the finishing step described below.

[0038] <Surfactants, pH adjusters, etc.> Here, a surfactant, a pH adjuster, etc. can be added to the water bath used in the reduction step S10, the water bath used in the crosslinking step S20, and the water bath used in the oxidation step S30, as necessary. As the surfactant, an anionic, nonionic, or cationic surfactant can be used. The concentration of the surfactant in the water bath can be 0.1 to 1 mass%, and preferably 0.2 to 0.5 mass%. As the pH adjuster, an acidic compound such as formic acid, acetic acid, citric acid, hydrochloric acid, or sulfuric acid, or a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium hydrogen carbonate can be used. The pH of the water bath used in the reduction step S10 and the oxidation step S30 is preferably 2 to 6, and more preferably 3 to 5. The pH of the water bath used in the crosslinking step S20 is preferably 8 to 12, and more preferably 9 to 11.

[0039] <Finishing process> The continuous manufacturing method of the shape-memorized wool fiber product according to the present embodiment includes a finishing step S40 in which the fourth precursor product is washed with hot water and dried to obtain a shape-memorized wool fiber product. The finishing step S40 is a step in which the fourth precursor product to which the shape-memory property has been imparted is washed with hot water and dried in order to make the wool fiber product in a state suitable for distribution. In the continuous manufacturing method, the reduction step S10, the crosslinking step S20, the oxidation step S30, and the finishing step S40 are continuously performed in this order.

[0040] In the finishing step S40, specifically, the fourth precursor product to which the shape memory property has been imparted is immersed in a water bath at 20 to 100°C, preferably 30 to 50°C, for 1 minute or more and less than 10 minutes, and the crosslinking agent, oxidation agent, reduction agent, and other compounds remaining in the fourth precursor product are washed away. Furthermore, the fourth precursor product washed with hot water is dried at a temperature of 70 to 90°C using a conventionally known high-temperature drying atmosphere (for example, a conventionally known drum dryer, etc.). As a result, a wool fiber product that can sustainably obtain a soft texture, feel, etc. by shape memory can be produced.

[0041] <Other processes> The continuous manufacturing method of the shape-memory wool fiber product according to the present embodiment can include other steps as necessary in addition to the reduction step S10, the crosslinking step S20, the oxidation step S30, and the finishing step S40. For example, the manufacturing method can include a step of scouring the first precursor product with a surfactant (scouring step) as a step performed before the reduction step S10.

[0042] This refining step can be carried out by immersing the first precursor product in a water bath containing a nonionic surfactant at 20 to 100°C for 5 to 30 minutes, thereby removing particulate matter such as dust and dirt contained in the first precursor product.

[0043] The above manufacturing method may include a rinsing step for washing away the reducing agent in the second precursor product after the reduction step S10 and before the crosslinking step S20. In the rinsing step, the second precursor product is immersed in a water bath at 40 to 100°C, preferably 40 to 80°C, for 1 minute or more and less than 10 minutes to wash away the reducing agent and other compounds remaining in the second precursor product. Furthermore, the above manufacturing method may include a second rinsing step for washing away the crosslinking agent in the third precursor product after the crosslinking step S20 and before the oxidation step S30. In the second rinsing step, the third precursor product is immersed in a water bath at 10 to 60°C, preferably 30 to 50°C, for 1 minute or more and less than 10 minutes to wash away the epoxy compound and other compounds remaining in the third precursor product.

[0044] The above-mentioned manufacturing method may include a step (fixing step) of treating the fourth precursor product with an aqueous solution containing both or either of acetic acid and the above-mentioned oxone, as a step after the oxidation step S30 and before the finishing step S40. Specifically, in the above-mentioned fixation step, the fourth precursor product can be immersed in an aqueous solution containing both or either of acetic acid and the above-mentioned oxone for about 1 to 10 minutes to carry out the above-mentioned treatment. This makes it possible to firmly fix the disulfide bonds of the recombined cystine in the wool fiber, thereby making it possible to produce a wool fiber product with a good yield that can continuously obtain a soft texture and the like by shape memory. The respective concentrations of acetic acid and hydrogen peroxide in the above-mentioned fixation step can be adjusted to appropriate concentrations for the purpose of the above-mentioned fixation.

[0045] Furthermore, the above manufacturing method can include a step of applying an oil agent to the fourth precursor product for the purpose of increasing its soft texture (texture improving step) after the oxidation step S30 and before the finishing step S40. Specifically, in the texture improving step, the fourth precursor product can be immersed for about 1 to 10 minutes in a solution containing a conventionally known additive (oil agent, silicon, or other additive) capable of imparting a soft texture, thereby enhancing the soft texture of the fourth precursor product, and thus enabling wool fiber products that can be manufactured with a higher yield and have a sustained soft texture due to shape memory.

[0046] <Action and effect> As described above, according to the method for continuously producing shape-memory wool fiber products of this embodiment, wool fiber products that can sustainably maintain a soft texture and the like due to shape memory can be continuously and efficiently produced.

[0047] [Shape-memory wool fiber products] The shape-memory wool fiber product according to this embodiment is a shape-memory wool fiber product containing wool fibers. The edges of the skin of the wool fibers are not melted, and the surface of the skin is not coated with resin. The image formed on the plane by projecting the wool fiber product 15g perpendicularly to the plane is 225 cm 2 Such wool fiber products can maintain their soft feel and texture by retaining their shape.

[0048] <Skin of wool fiber> The shape-memorized wool fiber product is a shape-memorized wool fiber product containing wool fibers as described above. The edges of the skin of the wool fibers are not dissolved, and the surface of the skin is not coated with resin. Here, the "edge" of the skin of the wool fiber refers to the tip part of the scaly skin called the cuticle or scale of the wool fiber that opens outward from the fiber axis. Furthermore, the surface of the skin "not coated with resin" means that a part or the whole of the scaly skin is not coated with vinyl polymers, other polymers, or silicone, which is a smoothing agent, which are conventionally known as chemical glues or molding agents.

[0049] FIG. 2 is a drawing substitute photograph showing an image of the edge of the epidermis of the wool fiber contained in the wool fiber product to which the Croy-Harcossett method is applied, taken by a scanning electron microscope. FIG. 3 is a drawing substitute photograph showing an image of the edge of the epidermis of the wool fiber contained in the shape-memorized wool fiber product according to this embodiment, taken by a scanning electron microscope. When a wool fiber product is obtained by performing a conventional process such as the Croy-Harcossett method, the edge of the epidermis of the wool fiber contained in the wool fiber product is dissolved by chlorine treatment as shown in FIG. 2, and the epidermis is fixed to the fiber axis by the above-mentioned polymer (resin) in order to align the direction of the epidermis along the fiber axis. This makes the wool fiber contained in the wool fiber product embrittled, thereby impairing the soft texture of the wool fiber product.

[0050] In contrast, the shape-memory wool fiber product according to this embodiment does not undergo the above-mentioned treatment in its manufacturing process, so that the edges of the skin of the wool fibers are not dissolved and the surface of the skin is not coated with resin, as shown in Fig. 3. This prevents loss of texture caused by the above-mentioned treatment. The fact that the edges of the skin of the wool fibers in the wool fiber product are not dissolved and the surface of the skin is not coated with resin can be identified by observing the skin part of the wool fibers of the wool fiber product at a magnification of 1000 to 2000 times (the magnification in Fig. 3 is 1500 times) using a scanning electron microscope (SEM).

[0051] <Soft texture and feel> In the shape-memorized wool fiber product, an image formed on a plane by projecting the wool fiber product 15g perpendicularly onto the plane has a diameter of 225 cm. 2 This makes it clear that the shape-memory wool fiber product has a larger volume (spread) per mass than conventional wool fiber products, and therefore it is understood that it has a soft feel, etc.

[0052] The method for measuring the area of ​​the "image" is as follows. First, a shape-memorized wool fiber product is obtained by following the above-mentioned continuous manufacturing method of a shape-memorized wool fiber product. Further, 15 g of a measurement sample is taken from the wool fiber product, and the measurement sample is placed on a commercially available graph paper on which squares of 1 cm length x 1 cm width are arranged. Next, a measurer looks at the measurement sample on the graph paper in a direction perpendicular to the graph paper from a position at least 30 cm away from the graph paper. As a result, the measurer's eyes see the graph paper with the squares blocked by the size of the measurement sample. Finally, the area of ​​the squares in the graph paper blocked by the measurement sample (hereinafter also referred to as the "area of ​​the blocked part") is calculated, and the value of the area of ​​the blocked part can be calculated as the value of the area of ​​the "image". Specifically, the area of ​​the shielding portion can be calculated by adding the area of ​​the square completely shielded by the measurement sample and the area of ​​the square only partially shielded by the measurement sample. The area of ​​the square only partially shielded is calculated by adding the area of ​​the square completely shielded by the measurement sample and the area of ​​the square only partially shielded. 2 , 0.5cm 2 , 0.75cm 2 The calculation shall be made by determining by eye which of the above is true.

[0053] The statue above is 230cm tall. 2 It is preferable that the image has an area of ​​240 cm or more. 2 The upper limit of the area of ​​the "image" is not particularly limited, but is, for example, 400 cm. 2 It is realistic to assume that the area of ​​the above "statue" is 225 cm 2 From the above, it is clear that the shape-memory wool fiber product has a larger volume (spread) per mass than conventional wool fiber products, and it is therefore understood that it has a soft texture, feel, etc. EXAMPLES

[0054] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0055] Example 1 [Manufacture of wool fiber products (wool TOP)] <Sample 1> (Reduction process) A second precursor product was obtained by immersing a commercially available merino wool TOP (fiber diameter: 19.5 μm) as a first precursor product containing wool fibers in a water bath containing 13 g of tris(hydroxypropyl)phosphine (product name: "Hishicolin P-540 (PP-40)" manufactured by Nippon Chemical Industry Co., Ltd.) per liter of water and 3 g of 68% by mass acetic acid per liter of water and at 80°C for 8 minutes. The second precursor product was removed from the water bath and dehydrated by 50% by mass with two rollers.

[0056] (Crosslinking process) The dehydrated second precursor product was immersed for 5 minutes in a water bath containing 5 g of ethylene glycol diglycidyl ether (product name: "Denacol EX810", manufactured by Nagase ChemteX Corporation) as an epoxy compound per liter of water and 6 g of soda ash per liter of water, and set at 40°C, to obtain a third precursor product. The third precursor product was removed from the water bath and dehydrated by 50% by mass with two rollers.

[0057] (oxidation process) The dehydrated third precursor product was immersed in a water bath containing 0.2 g of potassium peroxymonosulfate (product name: "Oxone", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) per liter of water, 3 g of 68% by mass acetic acid per liter of water, and 0.5 g of a chelating agent (product name: "Chilest NTB", manufactured by Chelest Co., Ltd.) per liter of water, and set at 40°C, to obtain a fourth precursor product. The fourth precursor product was taken out of the water bath and dehydrated by 50% by mass with two rollers. Furthermore, a texture improving process was carried out on this fourth precursor product using an oil agent, Worsted Oil (manufactured by Marubishi Yuka Kogyo Co., Ltd.) and Ohara Silicon O (manufactured by Ohara Palladium Chemical Co., Ltd.) as appropriate.

[0058] (Finishing process) The fourth precursor product was washed with water at 30° C. for 10 minutes and then dried in a drum dryer to obtain a shape-memorizing wool TOP of Sample 1.

[0059] <Sample 2> A shape-memory wool TOP of sample 2 was obtained in the same manner as sample 1, except that the amount of potassium peroxymonosulfate (product name: "Oxone", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) used in the oxidation process was changed to 10 g per liter of water.

[0060] <Sample 3> A shape-memory wool TOP of sample 3 was obtained in the same manner as sample 1, except that the amount of potassium peroxymonosulfate (product name: "Oxone", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) used in the oxidation process was changed to 0.02 g per liter of water.

[0061] <Sample A> The above-mentioned commercially available merino wool TOP (fiber diameter: 19.5 μm) was obtained as wool TOP for sample A.

[0062] <Sample B> The above-mentioned commercially available merino wool TOP (fiber diameter: 19.5 μm) was subjected to the conventionally known Kroy-Haako method, and then subjected to the same finishing process as sample 1 to obtain wool TOP of sample B.

[0063] <Sample C> The wool TOP of sample C was obtained by using the commercially available merino wool TOP (fiber diameter: 19.5 μm) described above in accordance with the method disclosed in Patent Document 1.

[0064] <Sample D> The wool TOP of sample D was obtained from the above-mentioned commercially available merino wool TOP (fiber diameter: 19.5 μm) according to the method disclosed in the above-mentioned Non-Patent Document 1.

[0065] 〔evaluation〕 <Evaluation of the epidermis in samples 1 to 3> First, the epidermis of the wool fibers in the shape-memorized wool tops of Samples 1 to 3 were observed at a magnification of 1500 times using a scanning electron microscope. As a result, it was confirmed that the edges of the epidermis of the wool fibers constituting the shape-memorized wool tops of Samples 1 to 3 were not dissolved and the above-mentioned epidermis was not covered with resin. Fig. 3 is a drawing substitute photograph showing an image of the edge of the epidermis of the wool fibers contained in the shape-memorized wool fiber product according to this embodiment taken by a scanning electron microscope, and specifically, it is an electron microscope image of the epidermis of the wool fibers constituting the shape-memorized wool top of Sample 1.

[0066] <Comparison of the soft texture of Sample 1 with Samples A to D> The soft texture of each sample was evaluated by comparing sample 1 and sample A, sample 1 and sample B, sample 1 and sample C, and sample 1 and sample D. Specifically, the above-mentioned measurement method was used to evaluate the area of ​​the image formed on the plane by projecting 15g of each sample perpendicularly to the plane. The results are shown in Table 1. Furthermore, images of sample 1 and sample A, sample 1 and sample B, sample 1 and sample C, and sample 1 and sample D arranged side by side and photographed are shown in Figs. 4 to 7. Fig. 4 is a drawing substitute photograph showing an image of the wool tops of sample 1 and sample A arranged side by side to explain the soft texture of the shape-memorized wool top of sample 1. Fig. 5 is a drawing substitute photograph showing an image of the wool tops of sample 1 and sample B arranged side by side and photographed to explain the soft texture of the shape-memorized wool top of sample 1. Fig. 6 is a drawing substitute photograph showing an image of the wool tops of sample 1 and sample C arranged side by side and photographed to explain the soft texture of the shape-memorized wool top of sample 1. FIG. 7 is a photograph showing the wool tops of sample 1 and sample D arranged side by side to illustrate the soft feel of the shape-memory wool top of sample 1. FIG.

[0067] [Table 1]

[0068] Example 2 The wool top of sample C was dyed by a conventional method, spun into yarn, and knitted to obtain the knitted fabric of sample C (spinning 2 / 36, twist number 510 / 285, flat knit 14 gauge). The shape-memorized wool top of sample 1 was also used to obtain the shape-memorized knitted fabric of sample 1 (spinning 2 / 36, twist number 510 / 285, flat knit 14 gauge) in the same manner as the knitted fabric of sample C. The appearances of these are shown in FIG. 8. FIG. 8 is a drawing-substitute photograph showing images of the knitted fabrics made from the wool tops of sample 1 and sample C arranged side by side to explain the soft texture of the knitted fabric made from the shape-memorized wool top of sample 1. From FIG. 8, it can be seen that the shape-memorized knitted fabric of sample 1 has a softer texture from its appearance than the knitted fabric of sample C.

[0069] <Consideration> From the above evaluation, it is understood that in sample 1, the edges of the skin of the wool fiber constituting sample 1 are not dissolved, and the skin is not covered with resin. Furthermore, it is understood that sample 1 has a softer texture than samples A to D. Moreover, sample 1 can be obtained by a continuous manufacturing method. It can also be assumed that samples 2 and 3 have properties equivalent to sample 1. From the above, samples 1 to 3 can continuously obtain a soft texture and the like by shape memory. Furthermore, samples 1 to 3 can be obtained by a continuous manufacturing method.

[0070] The embodiments and examples disclosed herein should be considered to be illustrative and not restrictive in all respects. The scope of the present invention is defined by the claims, not the above description, and is intended to include all modifications within the meaning and scope of the claims. [Explanation of symbols]

[0071] S10 reduction process, S20 crosslinking process, S30 oxidation process, S40 finishing process, 1 memory shaped wool TOP, 101, 102, 103, 104 wool TOP, 2 memory shaped knitted fabric, 203 knitted fabric.

Claims

1. A reduction step of treating a first precursor product containing wool fibers with a reducing agent containing a water-soluble organic phosphine compound to obtain a second precursor product; a crosslinking step of treating the second precursor product with a crosslinking agent containing an epoxy compound to obtain a third precursor product; an oxidation step of treating the third precursor product with an oxidation treatment agent containing a persulfate and / or a hydrogen persulfate to obtain a fourth precursor product; A finishing process of obtaining a shape-memorized wool fiber product by washing the fourth precursor product with hot water and drying it, A method for continuously producing a shape-memory wool fiber product, comprising the steps of: reducing, crosslinking, oxidizing, and finishing in this order.

2. 2. The method for continuously producing a shape-memory wool fiber product according to claim 1, wherein the processing time of the reducing step, the cross-linking step, the oxidizing step and the finishing step is less than 10 minutes each.

3. 3. A method for continuously producing a shape-memory wool fiber product according to claim 1 or claim 2, wherein in the oxidation step, the persulfate and / or hydrogen persulfate are used in a total amount of 0.001% by mass or more and 0.5% by mass or less relative to the mass of the third precursor product.

4. 3. The method for continuously producing a shape-memory wool fiber product according to claim 1, wherein the mass of the epoxy compound is 10 to 50 times the sum of the masses of the persulfate and the hydrogen persulfate.

5. 3. The method for continuously producing a shape-memory wool fiber product according to claim 1 or 2, wherein the wool fiber is a spun yarn having a fiber diameter of 13.5 μm or more and 33 μm or less, or wool TOP.

6. When the wool fiber is the spun yarn, the spun yarn is tubularly knitted, and 5 to 20 of the tubular knitted yarns are arranged in parallel to carry out the reduction step, the crosslinking step, and the oxidation step; A method for continuously manufacturing a shape-memory wool fiber product as described in claim 5, wherein when the wool fiber is the wool TOP, 6 to 40 of the wool TOPs are arranged in parallel to carry out the reduction step, the crosslinking step, and the oxidation step.

7. The method for continuously manufacturing a shape-memory wool fiber product according to claim 5, wherein, when the wool fibers are wool TOPs, the reducing step is carried out in a state where the wool TOPs are folded.

8. A shape-memory wool fiber product comprising wool fibers, The wool fibers have no dissolved edges of their skins and no resin-coated skins; The image formed on a plane by projecting the wool fiber product 15g perpendicularly to the plane is 225 cm 2 A shape-memory wool fiber product having an area of ​​at least 10 mm.

Images